Amorphous tetrafluoroethylene-hexafluoropropylene copolymers

ABSTRACT

Disclosed herein are novel amorphous tetrafluoroethylene-hexafluoropropylene (TFE-HFP) dipolymers, and other copolymers containing TFE, HFP and a third monomer, many of which are more random than previous amorphous TFE-HFP copolymers, as well as a novel high productivity continuous process for making these polymers. The polymers are particularly useful in the form of coatings, films and encapsulants.

This is a continuation-in-part of Ser. No. 08/596,932, filed on Feb. 5,1996 now U.S. Pat. No. 5,637,663, which is a continuation-in-part ofSer. No. 08/549,407 filed on Oct. 27, 1995 now U.S. Pat. No. 5,663,255,which is a continuation-in-part of Ser. No. 08/384,068, filed on Feb. 6,1995 now U.S. Pat. No. 5,478,905.

FIELD OF THE INVENTION

This invention concerns copolymers containing hexafluoropropylene andtetrafluoroethylene which are amorphous. They may be produced by a novelhigh pressure continuous process.

TECHNICAL BACKGROUND

Amorphous fluorinated polymers, particularly perfluorinated polymers,are highly useful, particularly as coatings and encapsulants, because oftheir unusual surface properties, low refractive index, low dielectricconstant, and the relative ease of coating or encapsulating objects withsuch polymers. However, the use of such polymers has been limitedbecause of their high cost, which usually derives from the high cost ofthe monomers and/or the high cost of the polymerization process to makethe polymers. Therefore, such polymers, and the processes for makingthem, which are lower in cost are constantly being sought.

U.S. Pat. No. 3,062,793 describes amorphous copolymers oftetrafluoroethylene (TFE) and hexafluoropropylene (HFP) which are madeby a high pressure free radical polymerization. The only processdescribed therein is a batch process which has a relatively lowproductivity.

SUMMARY OF THE INVENTION

This invention concerns a continuous polymerization process, comprising,contacting at a pressure of about 41 MPa to about 690 MPa, and atemperature above about 200° C., preferably about 200° C. to about 400°C., tetrafluoroethylene, hexafluoropylene, and a radical initiator, toproduce an amorphous polymer which contains at least 30 mole percent, ofrepeat units derived from said hexafluoropropylene, at least 1 molepercent of repeat units derived from said tetrafluoroethylene, andprovided that said continuous polymerization has an average residencetime of about 5 seconds to about 30 minutes.

This invention also concerns an amorphous polymer, consistingessentially of repeat units of the formula:

(a) at least about 30 mole percent of

    --CF.sub.2 --CF(CF.sub.3)--                                (I)

(b) at least about 1 mole percent

    --CF.sub.2 --CF.sub.2 --                                   (II)

and

(c) 0 to about 10 mole percent ##STR1##

wherein X is --C_(n) F_(2n+1) or --OC_(n) F_(2n+1), m is 2, 3 or 4, andn is either an integer of 2 to 20 with alkyl groups --CnF_(2n+1) or aninteger of 1-20 with alkoxy groups --OC_(n) F_(2n+1).

provided that in said polymer less than 20 mole percent of (I) ispresent in the form of triads.

The invention also concerns a continuous polymerization process,comprising, contacting at a pressure of about 41 MPa to about 690 MPa,and a temperature of about 200° C. to about 400° C.,tetrafluoroethylene, hexafluoropropylene, and a third monomer and aradical initiator, to produce an amorphous polymer which contains atleast 15 mole percent, preferably 30 mole percent of repeat unitsderived from said hexafluoropropylene, at least 0-70 mole percent ofrepeat units derived from said tetrafluoroethylene, and 0-70 molepercent of repeat units derived from said third monomer, and providedthat said continuous polymerization has an average residence time ofabout 5 seconds to about 30 minutes.

This invention also concerns a compound of the formula (C₄ F₉)₂ NSCF₃.

A novel compound herein is R⁶ R⁷ CFSO₂ R⁸ wherein R⁶ is perfluoroalkyl,perfluoroalkyl containing one or more ether oxygen atoms,perfluoroalkoxy or perfluoroalkoxy containing one or more ether oxygenatoms, R⁷ is perfluoroalkyl or perfluoroalkyl containing one or moreether oxygen atoms, and R⁸ is perfluoroalkyl. It is preferred that eachof R⁶, R⁷ and R⁸ independently contain 1 to 30 carbon atoms. It is alsopreferred that R⁸ is perfluoro-n-alkyl containing 1 to 20 carbon atoms.It is more preferred that R⁶ is perfluoro-n-propoxy, R⁷ istrifluoromethyl, and R⁸ is perfluoro-n-octyl. This compound is useful asan initiator for the polymerizations described herein.

Also disclosed herein is an amorphous polymer containing repeat unitsderived from:

27-60 mole percent hexafluoropropylene, up to 35 mole percent total ofone or more second monomers, and the balance tetrafluoroethylene,provided that at least one mole percent of TFE is present in thepolymer, and wherein said second monomer is ethylene, vinyl fluoride,trifluoroethylene, 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene,4-bromo-3,3,4,4-tetrafluoro-1-butene, CH₂ ═CHO(C═O)R² wherein R² isperfluoro-n-alkyl containing 1 to 8 carbon atoms, CH₂ ═CHR³ wherein R³is perfluoro-n-alkyl containing 1 to 8 carbon atoms, CH₂ ═CH(C═O)OR⁴wherein R⁴ is C_(n) F_(x) H_(y) wherein x+y=2n+1 and n is 1 to 8,chlorotrifluoroethylene, or allyltrimethoxysilane;

27-60 mole percent hexafluoropropylene, up to 5 mole percent total ofone or more fourth monomers and the balance tetrafluoroethylene,provided that the polymer contains at least 1 mole percenttetrafluoroethylene, wherein said fourth monomer isperfluorocyclopentene, perfluorocyclobutene, CF₂ ═CFCF₂ CN, CF₂ ═CFR⁵wherein R⁵ is perfluoroalkyl optionally containing one or more of one ormore ether groups, one cyano group, or one sulfonyl fluoride group,perfluoro(2-metylene-4-methyl-1,3-dioxolane),perfluoro(2-methyl-2,3-dihydro-1,4-dioxin), or FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂ ; or

up to 30 mole percent total of one or more second monomers and up to 5mole percent total of one or more fourth monomers.

Described herein is an amorphous copolymer, consisting essentially of:

(a) >15 mole percent of the repeat unit

    --CF(CF.sub.3)--CF.sub.2 --                                (I)

(b) at least 1 to about 60 mole percent of the repeat unit

    --CF.sub.2 --CF.sub.2 --                                   (II)

(c) about 0.1 to about 85 mole percent of the repeat unit

    --CH.sub.2 --CF.sub.2 --                                   (IV)

wherein no more than about 20 mole percent of (I) is present in triads.

Also described herein is an amorphous copolymer, consisting essentiallyof repeat units of the formula:

(a) >15 mole percent of the repeat unit

    --CF(CF.sub.3)--CF.sub.2 --                                (I)

(c) about 0.1 to about 85 mole percent of the repeat unit

    --CH.sub.2 --CF.sub.2 --                                   (IV)

wherein no more than about 20 mole percent of (I) is present in triads.

Described herein is an amorphous copolymer, consisting essentially of:

(a) >10 mole percent of the repeat unit

    --CF(CF.sub.3)--CF.sub.2 --                                (I)

(b) up to about 32 mole percent of the repeat unit

    --CF.sub.2 --CF.sub.2 --                                   (II)

(c) about 53 to about 85 mole percent of the repeat unit

    --CH.sub.2 --CF.sub.2 --                                   (IV)

wherein the sequence

    --(CH.sub.2 CF.sub.2)--(CH.sub.2 CF.sub.2)--(CF.sub.2 CH.sub.2)--(S1)

is present in an amount according to an equation

    mole percent S1≧0.23 (mole percent VF2 in polymer)-10.2.

DETAILS OF THE INVENTION

The TFE/HFP copolymer made herein is amorphous. By an amorphous polymeris meant that the polymer has a heat of melting of less than 1 J/g whenmeasured by Differential Scanning Calorimetry (DSC) at a heating rate of10° C./min, in the case of a TFE/HFP dipolymer. This is measured on a"first heat", that is virgin polymer is heated to at least 300° C. inthe DSC (at 10° C./min), and the heat of melting, if any, is measured.In the case of terpolymers, where the residual third monomer is oftenremoved from the polymer by heating for about four hours, at 150° C., ina vacuum oven, DSC "second heats", at 10° C./min to at least 200° C.,were used.

These polymers are made via a continuous polymerization process in whichthe initial ingredients are fed to the reactor in an essentiallycontinuous manner and in which the product stream is essentiallycontinuously withdrawn at approximately the same rate at which theingredients are added. Such types of reactions are generally known tothe artisan, see for instance H. F. Mark, et al., Ed., Kirk-OthmerEncyclopedia of Chemical Technology, 3rd Ed., vol. 19, John Wiley &Sons, New York, 1982, p. 880-914. Such continuous reactors includecontinuous stirred tank reactors and pipeline (tubular) reactors. Underthe conditions employed in the process as described herein, theproductivity of the process is exceptionally high. By productivityherein is meant the weight of polymer produced in a unit volume ofreactor in a unit volume of time. Productivities herein are reported askg/L/hr.

The process described herein has typical productivities of about 0.8 toabout 15 kg/L/hr. The Examples illustrate that typically higherpolymerization temperatures give higher productivities. By contrast, abatch polymerization, making a somewhat similar polymer, reported inU.S. Pat. No. 3,062,793, has productivities (from the Examples) of about0.01 to about 0.03 kg/L/hr, more than an order of magnitude less thanthat for the continuous process. This means a lower cost for polymerproduced by the continuous process.

The process is run at a pressure of about 41 to about 690 MPa (˜6,000 to˜100,000 psi), preferably about 55 to about 172 MPa (˜8,000 to ˜25,000psi), more preferably about 62 to about 152 MPa (˜9,000 to about 22,000psi), and especially preferably about 69 to about 103 MPa (˜10,000 to˜15,000 psi). As pressure drops down towards 41 MPa the molecular weightof the polymers formed and the conversion of monomers to polymer bothtend to drop.

It is preferred that solvents not be used in the process, since at thesepressures the monomers, particularly HFP, usually dissolve the polymer.Nonetheless, solvents can be used in the reactor. If the final productis to be a polymer solution, making the polymer solution directly may bepreferable, to reduce costs (see Example 43). Sometimes for conveniencein handling, small quantities of initiator are best introduced whendiluted to a larger volume with a small amount of solvent (see Example51). Solvent may also be used for other reasons, such as to decrease theviscosity of the process mixture, or to help keep lines clear ofpolymer, particularly at lower pressures. When solvents are used it ispreferred that they be essentially inert under process conditions.Useful solvents include perfluorodimethylcyclobutane andperfluoro(n-butyltetrahydrofuran).

The polymer is soluble in the monomer(s) under the process conditions.Therefore, one method of polymer isolation is to reduce the pressurebelow that required for solution of the polymer, and isolate the polymerfrom that, as by decantation, filtration or centrifugation. Indeed, itmay not be necessary to reduce the pressure of the unreacted monomers toatmospheric pressure, but merely that required for phase separation ofthe polymer. Therefore these monomers can be recycled with only a"partial" repressurization, thereby saving energy costs. Alternativelythe pressure can be reduced to atmospheric pressure, while the volatilemonomers are vented off, leaving the product polymer. The monomers canof course be recovered and reused.

The apparatus for running the polymerization may be any suitablepressure apparatus in which the reactant and products streams may beadded and removed at appropriate rates. Thus the apparatus may be astirred or unstirred autoclave, a pipeline type reactor, or othersuitable apparatus. Agitation is not necessary, but preferable,especially to obtain polymers with low MWD's. The material ofconstruction should be suitable for the process ingredients, and metalssuch as stainless steel are often suitable.

The polymerization is carried out above about 200° C., preferably fromabout 200 to about 400° C., more preferably from about 225 to about 400°C., and most preferably from about 250 to about 400° C. The initiator ischosen so that it will generate active free radicals at the temperatureat which the polymerization is carried out. Such free radical sources,particularly those suitable for hydrocarbon vinyl monomers at much lowertemperatures, are known to the artisan, see for instance J. Brandrup, etal., Ed., Polymer Handbook, 3rd Ed., John Wiley & Sons, New York, 1989,p. II/1 to II/65. The preferred temperature for running our processdepends on both the monomers and the initiator and is often a compromisebetween raising temperature to favor high productivities and highconversions and lowering temperature to minimize chain transfer andmonomer degradation. For the copolymerization of HFP with TFE, forexample, where chain transfer is not a problem, C₂ F₅ SO₂ C₂ F₅initiation is a good choice on account of the very high productivitiesit affords at 400° C. For the polymerization of HFP/TFE/PMVE, however,where PMVE chain transfer is of prime concern, NF₃ which retains goodefficiency at 250° C., is an excellent choice for initiator.

Suitable free radical initiators include NF₃, R_(f) NF₂, R_(f2) NF,R_(f3) N, R¹ N═NR¹, R_(f) OOR_(f), perfluoropiperazine, and hinderedperfluorocarbons of the formula C_(n) F_(2n+2) such as are described inWorld Patent Application 88/08007, wherein each R_(f) is independentlyperfluoroalkyl, preferably containing 1 to 20 carbon atoms, hinderedperfluoroalkenes of the formula C_(n) F_(2n), perfluoro(dialkylsulfones)of the formula R¹ SO₂ R¹, perfluoroalkyl iodides of the formula R¹ I, R¹SO₂ F, R¹ SO₂ Cl, ClSO₂ Cl, perfluoroalkylene diiodides of the formulaIR⁶ I where the two iodides are not vicinal or geminal wherein R⁶ isperfluoroalkylene containing 3 to 20 carbon atoms,perfluoro(dialkyldisulfides) R¹ SSR¹, and perfluoroalkyl compoundscontaining nitrogen-sulfur bonds of the formula R¹ ₂ NSR¹, wherein eachR¹ is independently saturated perfluorohydrocarbyl optionally containingone or more ether groups, isolated iodine, bromine or chlorinesubstituents, or perfluoroamino groups. By "saturatedperfluorohydrocarbyl" is meant a univalent radical containing onlycarbon and fluorine and no unsaturated carbon-carbon bonds. By an"isolated" iodine, bromine or chlorine substituent is meant that thereare no other iodine, chlorine of bromine atoms on carbon atoms alpha orbeta to the carbon atom bonded to the isolated iodine, bromine orchlorine atom. All of these initiators are illustrated in one or more ofthe Examples. Some of these initiators may only be active at the higherend of the temperature range of the polymerization process. This too isillustrated in the Examples, and the activity of any particularinitiator molecule may be readily determined by minimal experimentation.Preferred initiators are NF₃ R_(f2) NF, R_(f) NF₂, perfluoropiperazine,perfluoro(dialkylsulfones), i.e. R¹ SO₂ R¹, and hinderedperfluorocarbons. NF₃ is an especially preferred initiator. If highermolecular weight polymers are desired, the initiator should preferablynot have any groups present in its structure that cause any substantialchain transfer or termination during the polymerization. Such groupsusually include, for instance, organic bromides or iodides orcarbon-hydrogen bonds.

The amount of free radical initiator used will vary depending on processconditions. Generally speaking an effective amount is used, an effectiveamount being that which causes more polymerization to take place withthe initiator than without. It is likely that any polymerization withoutdeliberately added initiator present is due to adventitious impuritieswhich can act as initiators at the high polymerization temperatures.Effort should be made to minimize these impurities, such as oxygen. Auseful range of initiator concentration has been found to be about 0.003to about 0.5 g of initiator/kg monomer, preferably about 0.1 to about0.3 g/kg. Higher or lower amounts are also useful depending upon theinitiator, the monomers, goal molecular weights, process equipment, andprocess conditions used, and can readily be determined byexperimentation. The initiator may be added to the reactor as a solutionin the monomer(s).

While "solvents" may be added to the polymerization so that thepolymerization is carried out in solution or slurry, it is preferred iflittle or no solvent is added. The polymer formed is often soluble inthe supercritical HFP under the process conditions. The polymer may beisolated simply by reducing the pressure below about 34 MPa (˜5,000psi), at which point the polymer becomes insoluble. The polymer may alsobe isolated as fibers or fibrils by flash spinning from solvent and bydirect flash spinning of the polymerization mixture. Small amounts ofsolvents may be used for convenience, as for a carrier for theinitiator. FC-75, perfluoro(2-n-butyltetrahydrofuran), and the cyclicdimer of HFP are examples of useful solvents. Another useful solvent issupercritical CO₂.

The polymer produced by the instant process is amorphous. Whether thistype of a polymer would be amorphous depends on the composition(relative amounts of HFP and TFE and other monomers if present), and thedistribution of the two repeat units in the polymer. If a dipolymer, thepolymer product should preferably contain at least about 30 mole percentof (I) and at least 1 mole percent of (II), preferably at least 30 molepercent of (II), more preferably about 35 to about 50 mole percent of(1) and about 50 to about 65 mole percent of (II) when a dipolymer ismade [no repeat unit (III) present]. Optionally up to about 10 molepercent of repeat unit (III) may be present. When (III) is present apreferred composition is about 35 to about 65 mole percent (I), about 35to about 65 mole percent (II), and about 0.1 to about 10 mole percent of(III). Various comonomers (III) may be used in the polymerizationprocess, and be incorporated into the polymer. Perfluoro(alkyl vinylethers) and perfluorinated terminal alkenes, each optionally substitutedwith ether, cyano, halo (other than fluorine), sulfonyl halide, hydrogenor ester groups may be used. Also unfluorinated or partially fluorinatedolefins or vinyl ethers, optionally substituted as above, may also beused. Useful comonomers include CF₂ ═CFOCF₂ CF(CF₃)OCF₂ CF₂ SO₂ F,ethylene, propylene, isobutylene, vinylidene fluoride, vinyl fluoride,trifluoroethylene, 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene,4-bromo-3,3,4,4-tetrafluoro-1-butene,perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene), CF₂ ═CF(CF₃)COF, CH₂═CHO(C═O)R² wherein R² is perfluoro-n-alkyl containing 1 to 8 carbonatoms, CH₂ ═CHR³ wherein R³ is perfluoro-n-alkyl containing 1 to 8carbon atoms, CH₂ ═CH(C═O)R⁴ wherein R⁴ is C_(n) F_(x) H_(y) whereinx+y=2n+1 and n is 1 to 8, allyltrimethoxysilane, perfluorocyclopentene,perfluorocyclobutene, CF₂ ═CFCF₂ CN, CF₂ ═CFR⁵ wherein R⁵ isperfluoroalkyl optionally containing one or more of one or more ethergroups, cyano groups, and/or sulfonyl fluoride groups and preferablyonly one cyano or sulfonyl fluoride is present,perfluoro(2-methylene-4-methyl-1,3-dioxolane),perfluoro(2-methyl-2,3-dihydro- 1,4-dioxin), FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂, methyl vinyl ether, CFCl═CF₂, CH₂ ═CFCF₃, CH₂ ═CHCF₃, CH₂═CHCF₂ CF₂ CF₂ CF₃, CH₂ ═CHCF₂ CF₂ Br, CF₂ ═CFCF₂ CN, and CF₂ ═CFCF₂OCF₂ CF₂ SO₂ F. In preferred compounds R² is trifluoromethyl, R³ istrifluoromethyl or perfluoro-n-butyl, R⁴ is1,1,1,3,3,3-hexafluoroisopropyl, and R⁵ is --CF₂ CN.

The above monomers (and others) can be used to make copolymerscontaining repeat units derived from HFP, TFE and one or more of theabove monomers of the following compositions, and in these compositions:

>30 mole percent HFP, up to 25 mole percent X with the balance TFE,provided the polymer contains at least 1 mole percent TFE, wherein X isethylene propylene, isobutylene, or methyl vinyl ether;

>15 mole percent HFP, 0.1 to 85 mole percent vinylidene fluoride, and upto 60 mole percent TFE (note that this polymer may also be a dipolymerof HFP and vinylidene fluoride), preferably >20 mole percent HFP, 0.1 to75 mole percent vinylidene fluoride and up to 60 mole percent TFE, andmore preferably >30 mole percent HFP, 0.1 to 65 mole percent vinylidenefluoride and up to 60 mole percent TFE;

>30 mole percent HFP, up to 2 mole percent CF₂ ═CF(CF₃)COF, with thebalance TFE, provided the polymer contains at least 1 mole percent TFE;

27-60 mole percent HFP, up to 35 mole percent X, and the balance TFEprovided that at least one mole percent of TFE is present in thepolymer, wherein X is vinyl fluoride, trifluoroethylene,3,3,3-trifluoropropene, ethylene 2,3,3,3-tetrafluoropropene,4-bromo-3,3,4,4-tetrafluoro-1-butene, CH₂ ═CHO(C═O)R² wherein R² isperfluoro-n-alkyl containing 1 to 8 carbon atoms, CH₂ ═CHR³ wherein R³is perfluoro-n-alkyl containing 1 to 8 carbon atoms, CH₂ ═CH(C═O)OR⁴wherein R⁴ is C_(n) F_(x) H_(y) wherein x+y=2n+1 and n is 1 to 8,chlorotrifluoroethylene, and allyltrimethoxysilane, and preferredpolymers contain 30-50 mole percent HFP, up to 20 mole percent X and thebalance TFE, and more preferred polymer contain 30-45 mole percent HFP,up to 10 mole percent X and the balance TFE.

27-60 mole percent HFP, up to 5 mole percent X and the balance TFEprovided that the polymer contains at least 1 mole percent TFE, whereinX is perfluorocyclopentene, perfluorocyclobutene, CF₂ ═CFCF₂ CN, CF₂═CFR⁵ wherein R⁵ is perfluoroalkyl optionally containing one or more ofone or more ether groups, one cyano group, or one sulfonyl fluoridegroup, perfluoro(2-metylene-4-methyl-1,3-dioxolane),perfluoro(2-methyl-2,3-dihydro-1,4-dioxin), or FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂, and preferred polymers contain 30-50 mole percent HFP, up to 2mole percent X and the balance TFE.

In all polymers which contain a monomer other than HFP, TFE andvinylidene fluoride, it is preferred that minimum level of additionalmonomer is 0.05, more preferably 0.1 mole percent. Also more than onemonomer "X" may be present in any of the above polymers. When the"limitation" on any particular monomer or monomers "X" is a givenpercentage, the polymer may contain up to that percentage (total) ofthat "type" of monomer in the polymer. For example a copolymer maycontain up to 35 mole percent combined of trifluoroethylene and3,3,3-trifluoropropene, or another polymer may contain up to 5 molepercent CF₂ ═CFCF₂ CN and up to 30 mole percent 3,3,3-trifluoropropene.The total amount of "X" which may be in the copolymer may not exceed thehighest amount for any of the individual monomers, as given above.

Polymer containing HFP, vinylidene fluoride (VF2) and optionally TFE maybe analyzed by ¹⁹ F NMR to determine the microstructure of the polymer.In particular, the microstructure of monomer sequences of isolatedrepeat units derived from HFP and "surrounded" by monomer units derivedfrom VF2 may be determined. These are:

    ______________________________________                                        Sequence ID                                                                           Sequence No.                                                                             Sequence                                                   ______________________________________                                        β-β'(CH.sub.2)                                                              1          CH.sub.2 CF.sub.2 CF(CF.sub.3)CF.sub.2 CH.sub.2                               CF.sub.2                                                     β-γ'(CH.sub.2) 2 CH.sub.2 CF.sub.2 CF.sub.2 CF(CF.sub.3)CF.su                       b.2 CH.sub.2                                                 α-γ-γ'(CH.sub.2) 3 CH.sub.2 CF.sub.2 CF.sub.2                                CF(CF.sub.3)CH.sub.2 CF.sub.2 CH.sub.2 CF.sub.2                                α-β'(CH.sub.2) 4 CF.sub.2 CH.sub.2                                CF.sub.2 CF(CF.sub.3)CH.sub.2 CF.sub.2                       α-γ'(CH.sub.2); 5 CH.sub.2 CF.sub.2 CF.sub.2 CF(CF.sub.3)CH.                       sub.2 CF.sub.2 CF.sub.2 CF(CF.sub.3)                         δ(CF.sub.3)                                                           ______________________________________                                    

Herein the above sequences will be referred to by their Sequence No. Fordetermining these sequences, ¹⁹ F NMR spectra were acquired on 5%solutions in hexafluorobenzene (HFB). Spectra were taken at 80C on aBruker AC 250 operating at 235.4 MHz for 19F. The acquisition conditionsincluded a 90 degree pulse width of 5.0 μsec, 20 second recycle delay,and 64 co-added scans. Spectra were referenced to HFB at -162.46 ppm.

Composition was determined from the ¹⁹ F NMR spectrum in the followingway. Because of the high concentration of HFP, it was assumed that allVF2 next to HFP was represented by the signal at -75 ppm. VF2 which wasnon-adjacent to HFP was taken from the signal at -82 ppm. The sum ofthese areas was converted to moles of VF2. The amount of HFP wasdetermined from the sum of the areas at -75 ppm and -70 ppm, convertedinto moles of HFP. In samples containing TFE, the TFE was determinedfrom the area of the signals between -95 and -125 ppm corrected for CF₂s from HFP and corrected for the CF₂ s from VF2 represented in thesignal of HFP CF3s adjacent to CH₂ s from VF2 adjacent to CH₂ s fromVF2.

For at least one sample, the composition of VF2 determined in thismanner was confirmed by adding an internal standard oftrifluoromethyldichlorobenzene to a weighed amount of polymer anddetermining the amount of CF₂ from the ¹ H spectrum. For the sampletested, the results agreed within 3% relative.

HFP centered sequences were used as a way to identify differences inpolymerization. The ¹⁹ F signal at -179 to -179.5 ppm was identified asthe CF in an HFP centered VF2/HFP/VF2 sequence in which the CH₂ 's arebeta to the CF. The signal at -180.4 to -181.2 ppm was identified as aCF in a VF2/HFP/VF2 sequence in which there were one CH₂ alpha and oneCH₂ beta to the CF in the HFP. The final signal at -181 to -181.8 ppmwas identified as VF2/HFP/VF2 in which one CH₂ is alpha and one CH₂ isgamma and one CF₃ is delta to the CF.

Amorphous polymer containing HFP, VF2, and optionally TFE or othermonomers, but preferably only TFE, may also be analyzed by ¹³ C NMR.These analyses may yield additional information about these polymers. Inparticular, VF2 centered sequences may be determined, see for instanceF. A. Bovey, et al., Macromolecules, vol. 10, p. 559 et seq. (1977), andR. E. Cais, et al., Analytica Chimica Acta, vol. 189, p. 101 et seq.(1986), both of which are hereby included by reference. In particularthe sequence

    --(CH.sub.2 CF.sub.2)--(CH.sub.2 CF.sub.2)--(CF.sub.2 CH.sub.2)--(S1)

may be detected by its signal at 42.5 ppm (vs. hexafluorobenzeneinternal standard, see below for 13C NMR procedure). Any of the repeatunits in the polymers, including VF2 units, may be bonded to the end ofthis sequence. It has been found (see Examples 133 to 136, and their ¹³C analyses) that polymers containing 53 or more mole percent of VF2,preferably about 58 or more mole percent VF2, and about 10 or more molepercent HFP, preferably about 15 or more mole percent HFP, andoptionally containing TFE, made using the high pressure/high temperaturepolymerization processes described herein have a higher amount of thissequence than similar polymers made by "conventional" methods.

The mole percent of VF2 in S1 in the polymer, based on the total amountof VF2 in the polymer (from the ¹³ C analysis) is represented by theequation

    mole percent S1≧0.23 (mole percent VF2 in polymer)-10.2

More preferably, the mole percent of S1 is

    mole percent S1≧0.23 (mole percent VF2 in polymer)-9.8

All of the polymers herein may be crosslinked by methods known in theart. Perfluorinated polymers may be crosslinked by exposure to ionizingradiation. Polymers containing hydrogen or functional groups such asnitrile or sulfonyl halide may be crosslinked by methods known in theart. When crosslinked these polymers are of course crosslinkedelastomers if their Tg is below ambient temperature.

As mentioned above, the properties of the polymer will be affected notonly by the overall composition of the polymer, but by the distributionof the various monomer units in the polymer. The instant process yieldsa polymer in which the monomer units are more uniformly distributed inthe polymer, which gives polymer with more consistent properties. Onemeasure of polymer uniformity is randomness of the monomer units in thepolymer. A measure of this is relative amounts of isolated repeat units,diads, triads etc. By diads and triads are meant instances in which twoor three repeat units from the same monomer, respectively, occur in thepolymer.

Many of the polymers (including some of the polymers containing 3 ormore different repeat units) made by the process described herein haverelatively small amounts of triads of repeat unit (I), which of coursederived from HFP. Thus in such polymers less than 20 mole percent of (I)is in the form of triads, and preferably less than about 15% and morepreferably less than about 10%. As would be expected, in polymers withhigher amounts of (I), there is a tendency towards higher triad content.The amount of triads in the polymer can be determined by ¹⁹ F NMR (seebelow for procedure). See the summary of triad data for polymersprepared in Examples 23 and 33-36 in the table following Examples 45 to49. See Examples 23 and 33-36 and Comparative Example 1 for triadamounts in various polymers.

The instant polymers also have a narrower molecular weight distribution(MWD) than prior art polymers. By MWD is meant the weight averagemolecular weight divided by the number average molecular weight (Mw/Mn).Polymers described herein often have MWD's of less than 5, preferablyless than 4. Such polymers often have a better combination ofprocessability and physical properties.

Repeat unit (III) may be present to help suppress crystallization and/orlower a glass transition temperature, or for other purposes, and arederived from the corresponding α-perfluoroolefin, perfluorocycloolefinor perfluoro(alkyl vinyl ether). Preferred monomers for unit (III) inwhich --C_(n) F_(2n+1) is present are those in which --C_(n) F_(2n+1) isperfluoro-n-alkyl. When X is --C_(n) F_(2n+1) it is preferred if n is 2to 14, while if X is --OC_(n) F_(2n+1) it is preferred if n is 1 to 4,more preferably 1 or 3.

Since TFE is considerably more reactive in the polymerization than HFP,an excess of HFP is needed to achieve the desired polymer composition.Typically this also means that at the end of the polymerization, much orall of the TFE will have polymerized, but there will be (a considerableamount of) unpolymerized HFP. In a sense this is an advantage, since theHFP can act to help carry the polymer from the reactor, and noadditional carrier (such as a solvent) is needed. Typically the TFE willbe about 1 to 15 mole percent of the total amount of monomer being fedto the process, with the HFP and other monomer(s) (if present) being theremainder.

The average residence time is the average amount of time any of thematerial fed to the reactor actually spends in the reactor, and is afunction of the volume of the reactor and the volumetric flow of theprocess ingredients through the reactor. A preferred residence time isabout 20 sec to about 10 min, more preferably about 30 sec to about 5min, especially preferably about 40 sec to about 2 min. A minimumpreferred residence time is about 10 sec., more preferably about 15sec.. A maximum preferred residence time is 10 min.

When the process fluids are being added to the reactor, it is preferredif they are preheated just before they enter the reaction to atemperature somewhat less than that of the actual reactor temperature,about 20° C. to about 100° C. less. This allows one to maintain auniform constant temperature in the reactor itself, and for the newlyadded materials to start the polymerization reaction immediately uponentry to the reactor.

The amorphous polymers described herein are useful in a varietyapplications, many of which are related to the fact that the polymersare readily soluble in certain halogenated, especially perfluorinatedsolvents, and so the polymers are readily useable as films, coatings andencapsulants. Useful solvents include "dimer", perfluorobenzene,perfluoro(n-butyltetrahydrofuran), and FC-10 (tradename of "dimer" 3Mfluorocarbon fluid). Another type of useful solvent is a perfluorinated(organic) compound containing sulfur, such as perfluoro-1,4-dithiane,perfluorothiepane, perfluorodiethylsulfone, and perfluorooctanesulfonylfluoride.

In one preferred form, the solvent used to form solutions of theamorphous polymers herein is a mixed solvent. By a mixed solvent ismeant a solvent that contains two or more liquid compounds that aremiscible with each other in the proportion used. The compounds in themixed solvent need not be solvents for the amorphous polymer if usedalone, but it is preferred that at least one of the compounds of themixed solvent is a solvent for the amorphous polymer. It is preferredthat one of the compounds of the mixed solvent be a perfluorinatedcompound, as described in the preceding paragraph. Another preferredcompound is a hydrofluorocarbon or hydrochlorofluorocarbon as describedin Example 128. A preferred procedure for forming a solution of theamorphous polymer in a mixed solvent is to dissolve the amorphouspolymer in a perfluorinated compound, and then add the othercompound(s).

Since the polymers are relatively chemically resistant, they may be usedto encapsulate articles which must be protected from contamination,corrosion and/or unwanted adhesion to other materials. Films andcoatings may be particularly useful because of the inherent propertiesof the polymer, such as, lack of crystallinity (polymer is clear), lowsurface energy (and hence poor wetting by water or most organicliquids), low dielectric constant, low index of refraction, lowcoefficient of friction, low adhesion to other materials, etc.

The TFE/HFP copolymers (including di- and terpolymers) of this inventioncan be used in many ways. One use is as a processing aid in polyolefins.This aspect of the invention is discussed in detail below.

The TFE/HFP and TFE/HFP/(III) copolymer solutions and copolymer/solventsystems of this invention can be used in many ways, making it possibleto achieve end results that could not be achieved with previouslyavailable perfluoropolymers or could be achieved only in less convenientways. These results include any of the results for which polymersolutions are used, such as coating, encapsulation, impregnation, andthe casting of film. The copolymer solutions and copolymer/solventsystems of the invention can be employed in any of the methods by whichsolutions are known to be used, including dipping, painting, andspraying.

The copolymer solutions and copolymer/solvent systems of this inventioncan be used to make coatings on a broad range of substrate materials,including metal, semiconductor, glass, carbon or graphite, and naturaland synthetic polymers. The substrates can be in a broad range ofphysical forms, including film or paper, foil, sheet, slab, coupon,wafer, wire, fiber, filament, cylinder, sphere, and other geometricalshapes, as well as in a virtually unlimited number of irregular shapes.Coatings can be applied by methods known in the art, including dipping,spraying, and painting. For plane substrates of suitable dimensions,spin coating can be employed. Porous substrates can also be coated orimpregnated. These include, for example, screens, foams, microporousmembranes, and woven and non-woven fabrics. In making such coatings, thesolvent can be driven off by heat leaving a dry copolymer coating.Another advantage is that extremely thin coatings can be achieved, asthin as 100 angstroms or possibly even thinner depending on the coatingcharacteristics required.

Coatings of the copolymers of this invention can be a sole coating on asubstrate, or a component of a multilayer coating. For example, aTFE/HFP copolymer coating of this invention can be used as a first orprimer, intermediate, or final coating in a multilayer fluoropolymercoating system. The coatings of this invention include coatingsresulting from several successive applications of solution orcopolymer/solvent systems to increase coating thickness to desiredlevels.

Coatings of this invention can consist of the copolymers of thisinvention alone, or of the copolymers admixed with minor amounts ofother materials either soluble in the solvent or dispersed in thecoating solution, suspension, or copolymer/solvent system. A minoramount can be up to about 10 wt % based on the combined weight ofcopolymer and additive.

Specific coated articles are within the scope of this invention.

Coated articles include polymer extrusion dies and molds for rubber andplastic parts, such as o-rings, bottle caps, golf balls, golf ballcovers, golf ball cover half shells, and the like. The copolymers ofthis invention can be used in coatings. Both interior and exteriorsurfaces of extrusion dies may be coated to, respectively, facilitateextrusion and alleviate die drip buildup.

Coated articles include gasoline engine carburetor parts; internal partsof internal combustion engines such as valves and piston skirts; razorblades; metal containers such as cans, pans, trays, vessels, and thelike; metal sheets and foils; continuous metal belts, metal rods, tubes,bars, profiles, and the like; bolts, nuts, screws, and other fasteners.

Coated articles include an article bearing a machine-readable marking onat least one surface, especially but not limited to a tag that can beattached to another object to provide information about inventoryidentification, contents, ownership, hazards, operating conditions, ormaintenance requirements, for example.

Coated articles include wire for electrical and mechanical service. Ineither case, the metal wire may be solid or stranded. Wires formechanical service include catheter guide wire and the actuating wire ofpush-pull cable.

Coated articles include rubber o-rings, seals, beading, gasketing, fishhooks, and the like.

Coated articles include paper and textile materials, including wovenfabric including glass fabric, non-woven fabric, felts, and the like,fibers including filaments, yarns, e.g., staple and continuous filament,and strands.

Coated articles include foams, membranes, and the like.

Coated articles include optical fibers in which the substrate is a glassor plastic fiber.

Coated articles include semiconductors, semiconductor devices, magneticstorage media including disks, photoconductors, electronic assemblies,and the like, wherein the coating thickness may be as little as 200angstroms or even as little as 100 angstroms or even as little as 50angstroms. Use of solutions containing low concentrations of the TFE/HFPcopolymer of this invention, e.g., as low as 0.001 wt % copolymer can beespecially advantageous to form these very thin coatings.

One use for the TFE/HFP copolymers of this invention is as a processingaid in polyolefins. When the TFE/HFP copolymer of this invention is usedas a processing aid in the polyolefin for film applications, thepolyolefin generally will have a melt index (ASTM D-1238) of 5.0 or lessat 190° C., preferably 2.0 or less. For high-shear melt processing suchas fiber extrusion or injection molding, even high-melt-index resins,for example, those having a melt index of 20 or more, may sufferprocessing difficulties. Such polyolefins may comprise any thermoplastichydrocarbon polymer obtained by the homopolymerization orcopolymerization of one or more monoolefins of the formula CH₂ ═CHR'wherein R' is an alkyl radical, usually of not more than eight carbonatoms. In particular, this invention is applicable to the following:polyethylene, both of the high-density type and the low-density typehaving densities within the range 0.89-0.97; polypropylene;polybutene-1; poly(3-methylbutene); poly(4-methylpentene); and linearlow density copolymers of ethylene and an alpha-olefin, such aspropylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1,octadecene-1, or n-methylpentene-1.

Because of the different melt characteristics of the olefin polymersmentioned, the addition of the fluoropolymer process aids of thisinvention may be of greater value in some polyolefins than in others.Thus, polyolefins such as polypropylene and branched polyethylene, thathave low molecular weight or broad molecular weight distributions and,therefore, have good melt flow characteristics even at low temperature,may not require the use of the fluoropolymer additives or be noticeablyimproved by them, except under unusual, adverse extrusion conditions.However, for polymers such as high molecular weight, high densitypolyethylene or linear low density ethylene copolymers, particularlythose with narrow or very narrow molecular weight distributions,addition of the fluoropolymers is especially beneficial.

Such polyolefins are typically processed by extrusion techniques at meltprocessing temperatures T_(p) in the range of 175-275° C. Thecommercially important blown-film process is usually carried out atT_(p) in the range of 200-250° C., and commonly at 200-230° C.

The polyolefins and thus the polymer blend composition containing thefluoropolymer processing aid may contain assorted additives used in theart, such as but not limited to antioxidants, acid scavengers, lightstabilizers, pigments, slip agents, and lubricants. In particular,finely divided solids such as silica or talc may be incorporated asantiblock agents.

The concentration of fluoropolymer processing aid in the host resin atfabrication into the final article should be high enough to achieve thedesired effect in improving processibility, but not so high as to haveadverse economic impact. The amount required can vary with the effectdesired, the host resin, additives used in the host resin, and theprocessing conditions which may be different from the laboratoryconditions reported in the following examples. Under certain conditions,concentrations of 100 ppm or less, as low as 50 ppm or even 25 ppm, canbe effective. Under other conditions, the effective amount may be 1000,2000, or even 5000 ppm. For special purposes, concentrations of 10% oreven 25% may be appropriate. Thus from about 25 ppm to about 25% byweight of the fluoropolymer may be present, with preferred ranges beingfrom about 100 ppm to about 10% by weight, and even more preferable,about 100 ppm to about 2000 ppm by weight of the fluoropolymer. Thefluoropolymer processing aid can be incorporated into the host resin atthe desired final concentration, or can be incorporated into amasterbatch or concentrate that is added to the host resin in a ratiocalculated to yield the desired final concentration.

A novel compound herein is R⁶ R⁷ CFSO₂ R⁸ wherein R⁶ is perfluoroalkyl,perfluoroalkyl containing one or more ether oxygen atoms,perfluoroalkoxy or perfluoroalkoxy containing one or more ether oxygenatoms, R⁷ is perfluoroalkyl or perfluoroalkyl containing one or moreether oxygen atoms, and R⁸ is perfluoroalkyl. It is preferred that eachof R⁶, R⁷ and R⁸ independently contain 1 to 30 carbon atoms. It is alsopreferred that R⁸ is perfluoro-n-alkyl containing 1 to 20 carbon atoms.It is more preferred that R⁶ is perfluoro-n-propoxy, R⁷ istrifluoromethyl, and R⁸ is perfluoro-n-octyl. This compound is useful asan initiator for the polymerizations described herein.

In the Examples, the ¹⁹ F NMR, which is used to determine the HFPdistribution in the polymer, was measured on Bruker AC 250 NMR operatingat 235 MHz. Polymer samples were loaded in 5 mm NMR tubes and heated to250 to 360° C. in a narrow bore probe. In the melt, the methine CF's ofthe HFP units appear at -183.5 ppm if present as isolated units, at-179.5 if present as head to tail diads, and at -177 ppm if present ashead to tail triads. It is uncertain whether or not the integration forthe HFP triads at -177 ppm also includes higher (than triads) oligomericblocks. The amount of HFP triads was determined from the ratio of theareas of the ¹⁹ F NMR signal at -177 ppm to the total areas of thesignals at -177, -179.5 and -183.5 ppm.

In the Examples, ¹³ C NMR spectra were obtained using 20 weight percentsolutions of the polymers in hexafluorobenzene. Spectra were taken at60° C. on a Bruker AMX 360 spectrometer operating at 90.5 MHz, usingproton but not fluorine decoupling, 90° pulses, inverse gateddecoupling, a 30 second recycle delay, and taking 500-2000 coadded scansper sample. Vinylidene fluoride centered sequences were identified usingmuch the same methodology described in F. A. Bovey, et al.,Macromolecules, vol. 10, p. 559 et seq. (1977), and R. E. Cais, et al.,Analytica Chimica Acta, vol. 189, p. 101 et seq. (1986).

In the Examples, pressure change was used to calculate the weight oftetrafluoroethylene (TFE) added to the mixing reservoir (2). For thetetrafluoroethylene calculations in Examples 1-13, 50, 51 and 65, gaugepressure of TFE was incorrectly assumed to be absolute pressure. Basedupon this incorrect assumption the quantity 160 g of TFE was shown forExamples 1-13, 50, 51 and 65. The actual TFE added in these Examples wasabout 217 g to 228 grams. The actual amounts of TFE that were added areshown and labeled as such in parenthesis in Examples 1 and 50, 51 and65. The table on page 12 showing Examples 1-13 reflects the actual TFEmeasured.

In the Examples, the following abbreviations are used:

8CNVE--perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene)

Conv.--conversion

GPC--gel permeation chromatography

HFP--hexafluoropropylene

I.D.--inside diameter

IR--infrared (spectrum)

Mn--number average molecular weight

Mw--weight average molecular weight

Mv--viscosity average molecular weight

O.D.--outer diameter

PET--poly(ethylene terephthalate)

PMVE--perfluoro(methyl vinyl ether)

TFE--tetrafluoroethylene

TGA--thermogravimetric analysis

VF₂ or VF2--vinylidene fluoride

In the Examples, the following materials are used:

"dimer"-a perfluorinated solvent which is defined in U.S. Pat. No.5,237,049

FC-40--Fluorinert electronic liquid sold by 3M Industrial ChemicalsDivision, thought to be substantially perfluoro(tributylamine).

FC®-75--Fluorinert® Electronic Liquid, sold by 3M Industrial ChemicalsProducts Division, thought to be substantiallyperfluoro(2-butyltetrahydrofuran)

Kalrez® Perfluoroelastomer Parts--a tetrafluoroethylene/perfluoro(methylvinyl ether) and curesite monomer copolymer part available from E. I. duPont de Nemours and Company, Inc., Wilmington, Del., USA

Kapton® Polyimide Film--a polyimide film available from E. I. du Pont deNemours and Company, Inc., Wilmington, Del., USA

Mylar® Polyester Film--a poly(ethylene terephthalate) film availablefrom E. I. du Pont de Nemours and Company, Inc., Wilmington, Del., USA

Nordel® Hydrocarbon Rubber--an EPDM elastomer available from E. I. duPont de Nemours and Company, Inc., Wilmington, Del., USA

PET--poly(ethylene terephthalate)

Viton® Fluoroelastomer--a copolymer of vinylidene fluoride,hexafluoropropylene, and optionally tetrafluoroethylene made by freeradical polymerization in aqueous emulsion, in a continuous process, andavailable from E. I. du Pont de Nemours and Company, Inc., Wilmington,Del., USA

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic diagram of a High Pressure Continuous Unit whichcan be used for the continuous polymerization described herein. In FIG.1, within the barricade, NF₃ initiator is loaded into loop (1) and thenblown to reservoir (2) using hexafluoropropylene (HFP). In (2)tetrafluoroethylene is added to the HFP/NF₃ mixture, and the totalmixture in (2) is then removed from the bottom of (2), boosted to ahigher pressure and recirculated through the Monomer Recycle Loop, andthen part of it is sent to the heated (polymerization) reactor (5) andpart of it is recycled through valve (4) back to (2) after the pressureis lowered at pressure regulator (3) to the pressure of the contents of(2). After exiting reactor (5), the pressure of the mixture is reduced(often to atmospheric pressure) at back pressure regulator (6) and thecopolymer product is isolated in glass collection bottle (7). Gaseousmatter leaving the collection bottle is passed through meter (8) whichis used to measure the amount of unreacted gaseous monomers. A moredetailed description of the use of the apparatus of FIG. 1 appearsbelow.

EXAMPLE 1 Continuous Polymerization in 10 ml Autoclave with Agitation

All the reactants needed for a single run were premixed in a reservoir,pressured to 103 MPa, bled off through a heated pressure vessel atslightly lower pressure, and finally vented to atmospheric pressure inthe form of solid polymer foamed with unreacted monomer. The detailedprocedure given below for Example 1 is in reference to the reactorschematic, FIG. 1.

Preparation of Homogeneous Monomer/Initiator Mix

A 25 ml loop (1) off the feed line to a 3.8 L reservoir (2) waspressured to 710 kPa with nitrogen trifluoride at ambient temperature(˜0.6 g of NF₃). The 3.8 L reservoir was then loaded with 160 g of TFE(actual TFE loaded was 222 g) and 4000 g of HFP, a portion of the HFPbeing used to blow the NF₃ into the reservoir (2). Liquid monomer phasewas pulled off the bottom of the reservoir, pressured to 103 MPa, andthen recirculated back to the reservoir via back pressure regulator (3).The run was not started until the contents of the clave had been mixedby 10 minutes of such recirculation. Recirculation through the reservoirwas maintained for the duration of the run. No effort was made tocontrol the temperature of the reservoir which varied in the case ofthis run from 23° C. at the start to 33° C. at the finish.

Monomer Feed to Reactor

Flow was maintained through the system by letting monomer pressure downin stages, from 103 MPa in the recirculation loop to 96.5 MPa in thereactor and finally to atmospheric pressure in the product collector.The rate of flow was controlled by a micrometering valve (4) in thestainless steel line that connected the reservoir recirculation loop at103 MPa with the reactor at 96.5 MPa. Reactor pressure was maintained at96.5 MPa by back pressure regulator (6) placed after reactor (5).Micrometering valve (4) was opened until monomer flowed through thereactor at 10 to 12 g per minute, the measurement of flow rates beingdiscussed later. In order to maintain steady flow throughout the run,periodic adjustments were made to micrometering valve (4).

Reactor

As already mentioned, a flexible stainless steel tube, 0.40 cm O.D. by0.16 cm I.D., was run from micrometering valve (4) to the front end ofreactor (5). In an effort to bring the monomers up to reactortemperature rapidly, the last ˜61 cm of tubing before the reactor waswrapped with electrical tape and preheated to ˜200° C. Considering thatthe internal volume of this preheated segment is small relative to thereactor proper (˜1 ml in the preheated line vs. 10 ml in the reactor)and that reaction rates are slower at 200° C. than at 275° C., polymerformation in the preheated line was ignored for the purposes ofproductivity calculations. Reactor (5), in this Example a 10 ccstainless steel autoclave (10.2 cm long×1.1 cm I.D. and containing twoloose 0.63 cm stainless steel balls), was rocked vigorously with a paintshaker while heating to 275° C.

Product Isolation

A piece of flexible stainless steel tubing was run from reactor (5) toback pressure regulator (6) at which point pressure was dropped from96.5 MPa to atmospheric. In spite of the fact that no effort was made towarm either the line or the valve, no plugging was observed in this andthe majority of runs. When plugging did occur, it was most often at thelow pressure side of the regulator (6) where foamed polymer was leftwhen the monomer flashed off. To minimize plugging, the low pressureside of the let down valve was drilled out to provide as large anorifice as possible and then connected directly to a several liter glasscollection bottle (7). Gaseous monomer exiting the glass collectionbottle was passed through wet test meter (8), the liters of monomer perminute being converted to monomer flow in grams per minute. An averageflow rate of 10.9 g/min was thus observed over the 247 minute durationof this run. Given that the density of HFP at 275° C./96.5 MPa is ˜1.29g/ml, the average residence time for the monomers in reactor (5) was˜1.2 minutes. Polymer was recovered from the glass collection bottle (7)as large chunks of foamed white solid weighing 170.2 g. Pulling residualmonomer off with a vacuum pump reduced the weight of polymer to 159 gfor a productivity of 3.8 kg/L/hr. Fluorine NMR of the polymer melt at330° C. found 43 mole % (53 wt %) HFP copolymerized with 57 mole % (47wt %) TFE, allowing the calculation of 54% TFE conversion per pass and3.2% HFP conversion per pass. Rolling 1.5 g of this polymer with 5 ml ofFC-75 at room temperature gave a viscous solution. Transparent filmswere pressed at 160° C. by applying 3600 kg of pressure for 1 minute to1 g samples held between Kapton® polyimide film cover sheets. Under anapplied weight of 15 kg, a 2 g sample extruded through a melt indexer at0.63 g/minute at 200° C. GPC in FC-75 solvent showed Mw=235,000 andMn=94,700 for a Mw/Mn=2.87.

Characterization Summary

The results of Example 1 as well as of Examples 2 to 13 made under thesame conditions are tabulated below. Reproducibility was excellentconsidering that the process has yet to be automated.

    ______________________________________                                                 Polymer          Conv.                                                 Residence Wt % Melt Per Pass kg/ Mw/                                        Ex. Time     HFP.sup.1                                                                             Index.sup.2                                                                          HFP  TFE  L/hr Mn.sup.3                                                                           η.sub.inh.sup.4           ______________________________________                                        1   1.2 min  53%     0.6 g/min                                                                            3.2% 54%  3.8  2.87 0.39                            2 0.9 min 45% 0.4 g/min 2.4% 54% 4.2 3.65 0.45                                3 1.0 min 50% 0.3 g/min 2.6% 50% 3.9 3.53 0.54                                4 0.9 min 49% 0.5 g/min 2.2% 45% 3.7 3.63 0.49                                5 1.0 min 51% 0.4 g/min 2.5% 46% 3.8 3.23 0.49                                6 1.0 min 51% 0.6 g/min 2.7% 50% 3.9 3.34 0.51                                7 1.0 min 51% 1.3 g/min 2.6% 47% 3.8 3.12 0.41                                8 1.0 min 50% 0.7 g/min 2.5% 48% 3.6 2.99 0.44                                9 1.0 min 54% 1.0 g/min 2.7% 44% 3.6 3.83 0.29                                10 1.1 min 53% 0.7 g/min 3.1% 52% 3.8 2.85 0.41                               11 1.2 min 50% 0.8 g/min 3.1% 55% 3.7 2.62 0.39                               12 1.1 min 53% 0.7 g/min 2.8% 47% 3.5 2.45 0.48                               13 1.2 min 53% 1.0 g/min 3.1% 53% 3.6 2.57 0.41                             ______________________________________                                         .sup.1 Composition determined by fluorine NMR in the melt at                  300-340° C.                                                            .sup.2 Melt index determined at 200° C. with a 15 kg weight            .sup.3 Mw and Mn determined by GPC using FC75 solutions, versus linear        poly/hexafluoropropylene oxide) standards, one with Mn ˜20,000, the     other with Mn ˜70,000                                                   .sup.4 Inherent viscosity in FC75                                        

Comparative Example 1

An 85 ml autoclave was loaded with 60 ml of perfluorodimethylclobutaneand 0.25 g of cobalt trifluoride. The autoclave was sealed, chilled, andevacuated. Hexafluoropropylene was used to sweep in 4.25 g of TFE.Enough HFP was added to bring the pressure of the autoclave to 930 MPaat 23° C. (˜30 g of HFP). The autoclave was heated to 199° C. and 296MPa, an additional 6.9 MPa of HFP being added to match Eleuterio'scondition of 303 MPa. The autoclave was held at ˜200° C. for four hoursand then cooled and vented. The resulting polymer solution was filteredto get rid of pink residues (presumably containing insoluble cobaltcompounds), stripped to heavy oil on a rotary evaporator and then blowndown to 0.94 g of solid using a stream of nitrogen. This solid has aninherent viscosity of 0.207 in FC-75 closely matching Eleuterio'sExample II. Mw/Mn was 6.39, a very broad molecular weight distributioncompared to polymers made by our process. In a TGA analysis, thispolymer had lost 20% of its weight by 340° C.

    ______________________________________                                                   Polymer                                                              Residence Wt % Melt Conv. Per Pass                                          Ex.   Time     HFP     Index                                                                              HFP   TFE  kg/L/hr                                                                             Mw/Mn                            ______________________________________                                        Com. 1                                                                              240 min  57%     --   --    --   0.02  6.39                             ______________________________________                                    

EXAMPLES 14 TO 19 Continuous Polymerization in 10 mL Autoclave, With andWithout Agitation

The same set up was used as in Examples 1 to 13. About 80 to 90 gramsTFE, 200 g HFP and 0.6 g NF₃ were loaded to the mixing clave, making theratio of initiator relative to monomer about twice as great as inExamples 1 to 13, and reactor temperature was 300 to 325° C. instead of275° C. In all Examples but 14 the reactor was agitated by vigorousrocking. Product characterizations are shown below.

    ______________________________________                                                 Polymer          Conv.                                                 Residence Wt % Melt Per Pass                                                Ex. Time     HFP.sup.1                                                                             Index.sup.2                                                                          HFP  TFE  kg/L/hr                                                                             Mw/Mn.sup.3                       ______________________________________                                        NO SHAKING, 300° C.                                                      14    0.9 min. 51%    2 g/min                                                                             2.7% 64%  3.9   3.57                            SHAKING, 300° C.                                                         15    0.5 min. 46%   20 g/min                                                                             1.2% 36%  4.0   2.79                              16 0.7 min. 56%  2 g/min 2.7% 52% 4.4 2.12                                    17 0.9 min. 55% 20 g/min 4.1% 84% 5.5 3.60                                    18 1.9 min. 60% 20 g/min 5.4% 91% 3.2 2.41                                  SHAKING, 325° C.                                                         19    0.9 min. 60%    4 g/min                                                                             5.3% 86%  6.4   2.38                            ______________________________________                                         .sup.1 Composition determined by fluorine NMR in the melt at                  300-340° C.                                                            .sup.2 Ex. #14 melt index at 200° C. with 15 kg weight                 Ex. #15 melt index at 200° C. with 15 kg weight                        Ex. #16 melt index at 200° C. with 15 kg weight                        Ex. #17 melt index at 200° C. with 15 kg weight                        Ex. #18 melt index at 200° C. with 15 kg weight                        Ex. #19 melt index at 200° C. with 5 kg weight                         .sup.3 Mw and Mn determined by GPC using FC75 Solutions, versus linear        poly/hexafluoropropylene oxide) standards, one with Mn ˜20,000, the     other with Mn ˜70,000                                              

EXAMPLES 20 TO 44 Continuous Polymerization in Tube, No Agitation

The same set up was used as for Examples 1 to 13, except that in theseExamples reactor (5) was a 0.95 cm OD×0.52 cm ID×5.3 m long coil ofstainless steel tubing with an internal volume of ˜110 ml. The reactorcoil was heated using a sand bath. In view of the 5.3 m length of thetube no preheater was needed. Results for Examples 20 to 44 are shown inthe table below. Example 43 was unique in that 435 ml of liquid FC-75was added along with the initial monomer charge. The result of doingthis is that the product was obtained as ˜400 ml of solution containing0.16 g of dissolved polymer/ml.

    ______________________________________                                                      Weight % HFP                                                                            % Con-                                                                  Poly- version   kg/                                         Ex. ° C.                                                                           MPa    Res. Time                                                                            Feed  mer.sup.1                                                                           HFP  TFE  L/hr                          ______________________________________                                        ˜CONSTANT T, P, AND FEED                                                  20    250° C.                                                                        75.8 21 min.                                                                              98%   64%   2.9  81   0.2                           21 250° C. 75.8 9 min. 98% 61% 2.2 72 0.3                              22 250° C. 75.8 5 min. 98% 59% 2.2 76 0.5                              23 250° C. 75.8 4 min. 98% 58% 1.5 55 0.7                              24 250° C. 75.8 3 min. 98% 58% 1.3 37 0.6                            CONSTANT T, P, AND ˜TIME                                                  25    250° C.                                                                        96.5 6 min. 98%   58%   2.3  84   0.6                           26 250° C. 96.5 6 min. 96% 53% 3.8 84 0.9                              27 250° C. 96.5 6 min. 96% 54% 3.4 72 0.9                              28 250° C. 96.5 6 min. 96% 52% 3.2 74 0.9                              29 250° C. 96.5 6 min. 96% 53% 3.8 86 1.0                              30 250° C. 96.5 6 min. 95% 50% 4.3 80 1.1                              31 250° C. 96.5 6 min. 94% 44% 2.9 56 0.8.sup.2                        32 250° C. 96.5 8 min. 92% 47% 4.6 63 0.9.sup.2                      CONSTANT P, FEED, AND ˜TIME                                               33    275° C.                                                                        75.8 18 min.                                                                              98%   67%   3.3  85   0.2                           34 250° C. 75.8 21 min.  98% 64% 2.9 81 0.2                            35 225° C. 75.8 21 min.  98% 57% 1.7 65 0.1                            36 325° C. 96.5 6 min. 96% 59% 5.1 89 1.1                              37 300° C. 96.5 5 min. 96% 56% 5.4 ˜100 1.4                      38 275° C. 96.5 7 min. 96% 59% 5.2 90 1.0                              39 250° C. 96.5 6 min. 96% 53% 3.8 84 0.9                            CONSTANT T, FEED, AND ˜TIME                                               40    250° C.                                                                        62.0 5 min. 98%   59%   1.9  65   0.5                           41 250° C. 75.8 5 min. 98% 59% 2.2 76 0.5                              42 250° C. 96.5 6 min. 98% 60% 2.3 75 0.6                            IN THE PRESENCE OF FC-75 SOLVENT AND THIRD MONOMER,                             8CNVE                                                                         43    250° C.                                                                        96.5 ˜6 min.                                                                        90+%.sup.3                                                                          64%.sup.3                                                                           2.3  31   0.4                         IN THE PRESENCE OF THIRD MONOMER, PMVE                                          44    250° C.                                                                        96.5 ˜6 min.                                                                        94%.sup.4                                                                           47%.sup.4                                                                           3.1  ˜100                                                                         0.9                         ______________________________________                                         .sup.1 Composition detetmined by fluorine NMR in the melt at                  300-340° C.                                                            .sup.2 Incomplete removal of polymer from reactor, kg/L/hr probably large     than reported                                                                 .sup.3 Several percent 8CNVE, CF.sub.2 ═CFOCF.sub.2                       CF(CF.sub.3)OCF.sub.2 CF.sub.2 CN in feed. Polymer composition by fluorin     NMR: 63.8 wt % HFP, 34.1 wt % TFE, 2.1 wt% 8CNVE                              .sup.4 Starting mix: 94.3% wt % HFP, 3.8 wt % TFE, 1.9 wt % PMVE Polymer:     37.2 mole % HFP, 60.7 mole % TFE, 2.1 mole % PMVE                        

Molecular weight distributions were measured for only a few of thesamples made in the tubular reactor. Distributions appear to be a bitbroader and less uniform than experienced in the shaken autoclave(Examples 1-13 and 15-19) or the well-stirred reactor (Example 85).

    ______________________________________                                        Example             Mw/Mn                                                     ______________________________________                                        38                  4.96                                                        27 3.20 avg. of 2                                                             28 3.93 avg. of 2                                                             29 3.48 avg. of 2                                                           ______________________________________                                    

EXAMPLES 45 TO 49 Continuous Polymerization in Tube, No Agitation Effectof Decreasing Initiator

The same tubular reactor as described in Examples 20 to 44 was run at250° C./96.5 MPA with a residence time of 5.6 to 6.0 minutes and 2500 gHFP+50 g TFE+a variable amount of NF₃ added to the 3.8 L mixingreservoir. The effects of varying the amount of NF₃ in the startingmonomer mix is shown below.

    ______________________________________                                        Estimated     Wt % HFP    % Conversion                                        Ex.  Grams NF.sub.3 in Feed.sup.1                                                               Feed    Polymer                                                                             HFP   TFE  Kg/L/hr                            ______________________________________                                        45   0.7 g        98%     58%   2.3   84   0.6                                  46 0.4 g 98% 58% 1.6 56 0.4                                                   47 0.2 g 98% 60% 1.8 62 0.4                                                   48 0.1 g 98% 58% 1.5 54 0.3                                                   49 None 98% 57% 0.7 28 0.2                                                  ______________________________________                                         .sup.1 The grams of NF.sub.3 added to the monomer mixing reservoir were       estimated from PV = nRT. The amount of NF.sub.3 delivered to the reactor      for polymerization, however, may be quite a bit less if the highly            volatile NF.sub.3 concentrates in the vapor phases rather than in the         liquid monomer phase that is pumped to the reactor.                      

Initiation in the absence of NF₃ is probably the result of adventitiousoxygen. Shown immediately below are the results of ¹⁹ F NMR analysesgiving the percentages of HFP repeat units which are isolated, in diadsand in triads for certain Examples.

    ______________________________________                                                       % of Total CF's Found in                                         Polymer by .sup.19 F NMR                                                    Example #  Wt. % HFP Triads    Diads Isolated                                 ______________________________________                                        34         67%       12.40     41.47 46.13                                      35 64% 15.86 39.42 44.72                                                      23 59% 9.06 36.72 54.22                                                       36 57% 9.92 35.59 54.49                                                       33 47% 5.56 25.53 68.91                                                       Comparative 57% 26.63 27.26 46.4                                              Example #1                                                                  ______________________________________                                    

EXAMPLE 50

The agitated reactor was set up as in Example 1. Instead, however, ofusing NF₃ as the initiator, a solution of 0.8 ml ofperfluorodibutylamine [(C₄ F₉)₂ NF] dissolved in 5 ml of HFP cyclicdimer (perfluorodimethylcyclobutane) was introduced directly in the 96.5MPa reservoir 2 prior to the start of the run. A mix of this initiatorwith 160 g of TFE (actual TFE loaded was 223 g) and 4000 g of HFP wasrun through the 10 ml agitated reactor at 12 g/min at 275° C. (estimatedresidence time 1 minute) and 96.5 MPa for 315 minutes. This gave 146 gof poly(HFP/TFE), for a productivity of 2.8 kg/L/hr. The polymer wassoluble in FC-75 and found to have Mw=603,000, Mn=226,000, andMv=546,000. Fluorine NMR in the melt at 340° C. found 49 wt % HFP, 51 wt% TFE, and 74% of the methine FC's as triads. Conversion per pass was38% for TFE and 1.9% for HFP.

EXAMPLES 51-55

The agitated reactor was set up as in Example 1. Instead, however, ofusing NF₃ as the initiator, a solution of 1.5 g of perfluorodibutylamine[(C₄ F₉)₂ NF] dissolved in 5 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced directly in the 96.5 MPareservoir 2 prior to the start of the run. A mix of the initiator with160 g of TFE (actual TFE loaded was 222 g) and 4000 g of HFP was runthrough the 10 ml agitated reactor at 9.5 g/min at 325° C. (estimatedresidence time 1.2 min) and 96.5 MPa for 365 minutes. This gave 239 g ofpoly(HFP/TFE), for a productivity of 4.0 kg/L/hr. The polymer wassoluble in FC-75. Fluorine NMR in the melt at 320° C. found 54 wt %HFP/46 wt % TFE with 6.1% of the HFP methines as triads. GPC in FC-75found Mw=348,000, Mn=130,000, Mv=304,000. Inherent viscosity in FC-75was 0.413. Per pass conversions were 63% for TFE and 3.8% for HFP.

A major difference between NF₃ and (C₄ F₉)₂ NF is that (C₄ F₉)₂ NF is arelatively nonvolatile liquid. This means that when a mix of HFP, TFE,and (C₄ F₉)₂ NF is made in mixing reservoir 2, almost all of the (C₄F₉)₂ NF will reside in the liquid monomer phase. This in turn allows usto estimate with moderate accuracy how much (C₄ F₉)₂ NF was actuallyused as an initiator in this run: when 3472 g out of 4223 g (82%) ofstarting monomer mix was pumped through reactor 5, a like fraction ofthe (C₄ F₉)₂ NF, 82% or about 1.23 g, was probably used to initiatepolymerization. Knowing that 1.23 g of (C₄ F₉)₂ NF initiated 239 g ofpolymer with Mn=130,000 and assuming that there are two (C₄ F₉)₂ NFderived end groups per chain allows one to calculate that each (C₄ F₉)₂NF generated in fact 1.4 radicals. Generating 1.4 radicals out of apotential maximum of 2 [F• and (C₄ F₉)₂ N•] represents an initiatorefficiency of 70% for (C₄ F₉)₂ NF at 325° C. A similar calculation forExample 50 above shows that the efficiency of (C₄ F₉)₂ NF drops to about24% at 275° C.

Properties of the (C₄ F₉)₂ NF initiated polymer made here in Example 51are compared to those of closely bracketing NF₃ initiated runs (Examples52 to 55) made in the same equipment:

    __________________________________________________________________________    Gel Permeation Chromatography Data                                                                         .sup.19 F NMR Data                               Ex. #                                                                             Mw × 10.sup.-3                                                                Mn × 10.sup.-3                                                                Mw/Mn                                                                             Mv × 10.sup.-3                                                               IV  Wt % HFP                                                                            Triads                                     __________________________________________________________________________    52  334   129   2.59                                                                              292  0.411                                                                             53% HFP                                                                             6.5%                                         51 348 130 2.67 304 0.413 54% HFP 6.1%                                        53 371 142 2.99 326 0.443 50% HFP 5.3%                                        54 423 137 3.08 367 0.492 51% HFP 5.0%                                        55 451 156 2.90 397 0.517 48% HFP 3.2%                                      __________________________________________________________________________

EXAMPLE 56

The agitated reactor was set up as in Example 1. Instead, however, ofusing NF₃ as the initiator, 76 kPa (gauge) of CF₃ OOCF₃ (about 0.3 g)was introduced into a 25 ml initiator loop 1. A mix of this initiatorwith 160 g of TFE (actual TFE loaded was 221 g) and 4000 g of HFP wasrun through the 10 ml agitated reactor at about 10.6 g/min at 275° C.and 96.5 MPa for 340 minutes. This gave 53 g of poly(HFP/TFE), for aproductivity of 1.0 kg/L/hr. The polymer was soluble in FC-75 and foundto have Mw=852,000 and Mn=235,000.

EXAMPLE 57

A 50 wt % HFP copolymer of HFP and TFE, which had a melt viscosity at100 sec⁻¹ of 854 Pa.s was dissolved in a variety of solvents to testsolubility. To an Erlenmeyer flask fitted with a reflux condenser andmagnetic stirrer were added 95 g various solvents and 5 g polymer. Themixtures were heated on a hot plate with stirring until reflux occurred.The solvents tested were "dimer", FC-75, FC-40 and hexafluorobenzene.

The polymer dissolved in all solvents tested to form clear, lowviscosity solutions. When cooled to room temperature, all samplesremained as clear, low viscosity fluids.

EXAMPLE 58

The FC-75 solution of Example 57 was used to prepare dipped coatings onvarious metals. Metal coupons of size 2.5 cm×7.6 cm×0.64 mm were cleanedin an ultrasonic bath with acetone, dried at 150° C. for 4 hours, cooledto room temperature and dipped into the 5% solution. Excess solution wasdrained off. The coupons were dried overnight at 150° C. Metals testedwere copper, brass, aluminum, stainless steel, galvanized steel andchrome plated steel. All coatings were smooth and clear. The coppercoupon had some discoloration.

Contact angle measurements of a droplet of water on each coating weremade. Contact angles were 115° +/-2° advancing and 94° +/-2° receding,showing that the coatings were uniform and were hydrophobic.

Film thickness was measured for each coupon using a Tencor StylusProfilometer. Film thickness was 1.7 μm+/-0.5 μm.

Film adhesion was tested using ASTM D3359. Each coated film wasscratched in a cross hatch pattern of 10 lines per 2.5 cm using a razorknife edge. Adhesive tape was pressed against the cross hatch scoredfilm. The tape was removed and the film examined. No removal of polymerfilm from the metal coupon occurred. The cross hatched scored coatedfilms were placed in boiling water for 1 hour. The coupons were removedfrom the water, dried at 150° C. for 1 hour and were cooled to roomtemperature. An adhesive tape was again pressed against the cross hatchscored film and then removed. No removal of polymer film from the metalcoupon occurred. This shows that the coated films are strongly adheredto the metal coupons and can resist the action of boiling water.

EXAMPLE 59

The FC-75 solution of Example 57 was used to prepare dipped coatings onvarious polymers. Polymer strips of size 2.5 cm×7.6 cm×1.9 mm wereprepared from nylon 6,6, Nordel® hydrocarbon rubber vulcanizate,neoprene vulcanizate, Viton® fluorocarbon rubber vulcanizate, Kalrez®perfluorocarbon rubber vulcanizate, and strips of size 2.5 cm.×7.6cm×0.25 mm were cut from films of Mylar® PET and Kapton® polyimide (allof these products are available from E. I. du Pont de Nemours andCompany, Wilmington, Del., U.S.A.). All samples were cleaned in anultrasonic bath with acetone, dried at 150° C. for 4 hours, cooled toroom temperature and dipped into the 5% solution. Excess solution wasdrained off. The coated samples were dried overnight at 150° C. Allcoatings were smooth and clear.

Contact angle measurements of a droplet of water on each coating weremade. Contact angles were 115°+/-4° advancing and 94°+/-4° receding,showing that the coatings were uniform and were hydrophobic.

Film thickness was measured for coatings on nylon, Mylar® and Kapton®using a Tencor Stylus Profilometer. Film thickness was 1.7 μm+/-0.5 μm.Film adhesion was tested using ASTM D3359. Each coated film wasscratched in a cross hatch pattern of 10 lines per 2.5 cm using a razorknife edge. Adhesive tape was pressed against the cross hatch scoredfilm. The tape was removed and the film examined. No removal of thecoated film from the polymer surface occurred. The cross hatch scoredcoated strips were placed in boiling water for 1 hour. The strips wereremoved from the water, dried at 150° C. for 1 hour and were cooled toroom temperature. An adhesive tape was again pressed against the crosshatch coating and then removed. No removal of coating film from thepolymer strips occurred. This shows that the coated films are stronglyadhered to the polymer strips and can resist the action of boilingwater.

EXAMPLE 60

The solution of Example 57 in FC-75 was used to prepare dipped coatingson various fabrics. Pieces of fabric were cut to size 15.2 cm square.The fabrics were a loose woven nylon, a loose woven PET polyester, aloose woven cotton and a Nomex® felt. The fabrics were dipped into the5% solution and were squeezed by hand to remove excess solution. Thefabrics were dried for 1 hour at 150° C. After drying, all fabricsremained soft and flexible and were porous.

A drop of distilled water was placed on each fabric and on a portion ofthe same fabric that had not been treated. In each case, the water wetand penetrated the untreated fabric, but formed a spherical drop on thetreated fabric and did not penetrate. Thus, the treated fabrics werehydrophobic.

EXAMPLE 61

The solution of Example 57 in FC-75 was treated as a mold release agent.A size 214 O-ring mold was cleaned with Easy Off® commercial ovencleaning agent. The mold was washed with water and dried by heating in apress at 177° C. for 15 min. The mold had 30 sites for molding O-rings.Fifteen sites were spray coated with solution. The remaining sites werecoated with commercial mold release, McLube® No. 1725. The coatings weredried by placing the mold in a press at 177° C. for 15 min. Kalrez®O-ring preforms were placed in the proper sites and the mold was placedin a press at 177° C. for 15 min to mold the O-rings.

After the first molding cycle there was some sticking to the McLubecoated sites. The solution coated sites had no sticking. The mold cyclewas repeated for three additional cycles with no additional mold releasecoating applied to any of the sites. After the final molding cycle,about 30% of the O-rings removed from the sites lubricated with McLube®were torn during removal from the mold due to sticking. None of theO-rings removed from sites coated with solution were torn. There was nosticking of O-rings at the solution coated sites.

EXAMPLE 62

The solution of Example 57 in FC-75 was tested as a mold release agent.

A conventional golf ball compression mold was cleaned with "Easy Off"commercial oven cleaning agent. The mold was washed with water and driedby heating in a press at 204° C. for 15 min. The mold was spray coatedwith solution and was dried by placing the mold in a press at 204° C.for 4 hours. The mold cavity was filled with a Surlyn® ionomer golf ballcover and a spiral wound rubber core. The golf ball was compressionmolded for 15 min at 204° C.

When the mold was used without solution coating, the golf ball coveradhered to the metal mold and pulled away from the core when the ballwas removed from the mold. When the mold was coated with the solutionthere was no sticking and the molded golf ball was easily removed.

EXAMPLE 63

A linear low density polyethylene with melt index 1 g/10 min wasextruded through a capillary die of size 0.76 mm×2.5 cm×90° using anInstron® capillary rheometer. The shear stress required to extrude thepolyethylene at 220° C. at a shear rate of 347 sec⁻¹ was 4.0×10⁵ Pa. Thesurface of the extrudate was rough and distorted.

To the polyethylene was added TFE/HFP copolymer at a level of 0.1%. Theextrusion through the capillary die was repeated. When the polyethylenecontaining the TFE/HFP copolymer was extruded at 220° at a shear rate of347 sec⁻¹ the shear stress required was reduced to 2.0×10⁵ Pa, and theextrudate was smooth and was not distorted. Thus, the presence of thecopolymer reduced the shear stress required to extrude the polyethylenefrom 4.0×10⁴ Pa to 2.0×10⁴ Pa and the surface of the extrudate becamesmooth and undistorted. The TFE/HFP copolymer acted as a processing aidfor the polyethylene.

EXAMPLE 64

An 0.38 mm×9.5 mm×90° tungsten carbide capillary was coated with a 1%solution of TFE/HFP copolymer dissolved in FC-75. The coating was driedat 250° C. for 2 hours. A linear low density polyethylene, GRSN 7047from Union Carbide Corp., melt index 1 g/10 min, containing 2.5%colloidal silica (to act as an abrasive material) was extruded throughthe capillary die using an Instron capillary rheometer at a temperatureof 220° C. and at a shear rate of 833 sec⁻¹.

When the polyethylene was extruded through the capillary die with nosolution coating on the capillary, at a temperature of 220° C. and at ashear rate of 833 sec⁻¹ the shear stress required was 4.5×10⁵ Pa. Thesurface of the extrudate was rough and distorted. When the polyethylenewas extruded through the coated capillary under the same conditions, theshear stress required dropped to 2.5×10⁵ Pa shortly after start up andthe surface of the extrudate was smooth and undistorted. The shearstress slowly rose, over a period of about 2 hours to 4.5×10⁵ Pa, as thesolution coating was slowly worn away by the abrasive polyethylene. Whenthe shear stress reached a level greater than 3.0×10⁵ Pa the surface ofthe extrudate again became rough. This example shows that the solutioncoating on the capillary acted as an extrusion aid that significantlyreduced shear stress and eliminated surface roughness. When the coatingwas completely worn away, after two hours, the shear stress returned tothe uncoated value and surface roughness reappeared.

EXAMPLE 65 Polymerization in Presence of CO₂

The agitated reactor was set up as in Example 1, loading a mixture of3000 g of HFP, 160 g of TFE (actual: 226), 157 g of CO₂ diluent, and 1.5g of NF₃. This mixture was run through the 10 cc agitated reactor atabout 10 to 11 g/min at 300° C. and 96.5 MPa for 278 minutes. This gave254 g of polymer for a productivity of 5.5 kg/L/hr. The polymer had aninherent viscosity of 0.254 and a melt flow of 4 g/min at 200° C. undera load of 5 kg in a melt indexer.

EXAMPLES 66-84

Polymerizations in Examples 66 to 84 here were run in a semicontinuousfashion using the equipment and general methods described in Example 1.Initiator performance is compared in terms of grams or polymer made pergram of initiator. For this is used the formula: (grams ofpolymer)÷[(grams of initiator added to the mixing clave)×(fraction ofreaction mixture run through the polymerizer)]. Polymerizationtemperatures were measured using a thermocouple placed between the wallof the reactor and its heating jacket except in Example 85 in which casereactor temperature was measured internally. Example 85 also changes thereactor from a shaken tube to a larger, mechanically well-stirred vesselwith separately metered flows for the HFP, the TFE, and a HFP/NF₃mixture. The larger scale and the use of calibrated flow meters inExample 85, should make monomer feed ratios more accurate.

EXAMPLE 66 CF₃ CF₂ CF₂ C(CF₃)₂ NF₂ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.5 ml CF₃ CF₂ CF₂ C(CF₃)₂ NF₂ dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 114 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at 11 g /min at 275° C. (estimated residencetime 1.2 min) and 96.5 MPa (96.5 MPa) for 154 minutes. After vacuum pumpdrying at room temperature, this gave 51.1 g of poly (HFP/TFE) for aproductivity of 2.0 kg/L/hr. One gram of polymer was soluble in 5 ml ofroom temperature FC-75 with a trace of insoluble haze. Fluorine NMR inthe melt at 320° C. found 44 wt % HFP/56 wt % TFE with 1.3% of the HFPmethines as triads. GPC in FC-75 at 80° C. found Mw=629,000, Mn=251,000,Mv=566,000. Inherent viscosity in FC-75 at 25° C. was 0.365. Roughly 69g of polymer were made/g of CF₃ CF₂ CF₂ C(CF₃)₂ NF₂ initiator.

EXAMPLE 67 (CF₃)₂ CFN═NCF(CF₃)₂ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.3 ml (CF₃)₂ CFN═NCF(CF₃)₂ dissolved in2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) was introducedto 96.5 MPa reservoir 2 prior to the start of the run. A mix of thisinitiator with 115 g of TFE and 2000 g of HFP was run through the 10 mlagitated reactor at 11 g/min at 350° C. (estimated residence time 1.0min) and 96.5 MPa for 145 minutes. After vacuum pump drying at roomtemperature, this gave 77.6 g of poly (HFP/TFE) for a productivity of3.2 kg/L/hr. One gram of polymer gave a hazy, quite viscous solution in5 ml FC-75 at room temperature. Fluorine NMR in the melt at 340° C.found 53 wt % HFP/47 wt % TFE with 8.3% of the HFP methines as triads.GPC in FC-75 at 80° C. found Mw=599,000, Mn=229,000, Mv=541,000.Inherent viscosity in FC-75 at 25° C. was 0.540. Roughly 195 g ofpolymer were made per gram of (CF₃)₂ CFN═NCF(CF₃)₂ initiator.

EXAMPLE 68 (CF₃)₂ CFN═NCF(CF₃)₂ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.6 g (CF₃)₂ CFN═NCF(CF₃)₂ dissolved in2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) was introducedto 96.5 MPa reservoir 2 prior to the start of the run. A mix of thisinitiator with 114 g of TFE and 2000 g of HFP was run through the 10 mlagitated reactor at 12 g /min at 275° C. (estimated residence time 1.1min) and 96.5 MPa for 160 minutes. After vacuum pump drying at roomtemperature, this gave 59.7 g of poly (HFP/TFE) for a productivity of2.2 kg/L/hr. The polymer was soluble in FC-75. Fluorine NMR in the meltat 275° C. found 46 wt % HFP/54 wt % TFE with 2.1% of the HFP methinesas triads. GPC in FC-75 at 80° C. found Mw=477,000, Mn=124,000,Mv=413,000. Inherent viscosity in FC-75 at 25° C. was 0.614. Roughly 110g of polymer were made per gram of (CF₃)₂ CFN═NCF(CF₃)₂ initiator.

EXAMPLE 69 (CF₃)₂ CFN═NCBr(CF₃)₂ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.5 ml (CF₃)₂ CFN═NCBr(CF₃)₂ dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 116 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at 11 g/min at 275° C. (estimated residencetime 1.2 min) and 96.5 MPa for 110 minutes. After vacuum pump drying atroom temperature, this gave 50.5 g of poly (HFP/TFE) for a productivityof 2.7 kg/L/hr. One gram of polymer in 5 ml of room temperature FC-75gave a highly viscous, hazy solution in FC-75 with perhaps significantamounts of polymer still present as swollen gel. Fluorine NMR in themelt at 340° C. found 48 wt % HFP/52 wt % TFE with 5.0% of the HFPmethines as triads. GPC in FC-75 at 80° C. found Mw=569,000, Mn=185,000,Mv=508,000. Inherent viscosity in FC-75 at 25° C. was 0.557. Roughly 95g of polymer were made per gram of (CF₃)₂ CFN═NCBr(CF₃)₂ initiator.

EXAMPLE 70 N-Fluoroperfluoropiperidine Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.3 ml N-fluoroperfluoropiperidinedissolved in 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane)was introduced to 96.5 MPa reservoir 2 prior to the start of the run. Amix of this initiator with 115 g of TFE and 2000 g of HFP was runthrough the 10 ml agitated reactor at 14 g/min at 350° C. (estimatedresidence time 0.8 min) and 96.5 MPa for 110 minutes. After vacuum pumpdrying at room temperature, this gave 100.2 g of poly (HFP/TFE) for aproductivity of 5.4 kg/L/hr. The polymer was soluble in FC-75. FluorineNMR in the melt at 340° C. found 50 wt % HFP/50 wt % TFE with 2.6% ofthe HFP methines as triads. GPC in FC-75 at 80° C. found Mw=445,000,Mn=181,000, Mv=398,000. Inherent viscosity in FC-75 at 25° C. was 0.461.Roughly 230 g of polymer were made per gram ofN-fluoroperfluoropiperidine initiator.

EXAMPLE 71 CF₃ C(C₂ F₅)₂ CF(CF₃)₂ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 1.0 ml CF₃ C(C₂ F₅)₂ CF(CF₃)₂ dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 113 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at 10 g/min at 350° C. (estimated residencetime 1.1 min) and 96.5 MPa for 106 minutes. After vacuum pump drying atroom temperature, this gave 105.6 g of poly (HFP/TFE) for a productivityof 6.0 kg/L/hr. One gram of polymer gave a clear, attractive solution in5 ml of FC-75 at room temperature. Fluorine NMR in the melt at 340° C.found 58 wt % HFP/42 wt % TFE with ˜7% of the HFP methines as triads.GPC in FC-75 at 80° C. found Mw=199,000, Mn=93,000, Mv=179,000. Inherentviscosity in FC-75 at 25° C. was 0.247. Approximately 100 g of polymerwere made per gram of CF₃ C(C₂ F₅)₂ CF(CF₃)₂ initiator.

Running an identical polymerization but at 275° C. gave 73.4 g ofpolymer after 145 minutes with an average monomer flow rate of 11 g/min.This polymer analyzed for 50 wt % HFP/50 wt % TFE and 5.5% triads byfluorine NMR at 320° C.; Mw=239,000, Mn=82,900, and Mv=206,000 by GPC;inherent viscosity=0.391 at 25° C.; and a productivity of 3.0 kg/L/hr.Roughly 51 g of polymer were made per gram of initiator.

*CF₃ C(C₂ F₅)₂ CF(CF₃)₂ : 88% CF₃ C(C₂ F₅)₂ CF(CF₃)₂ and 12% [(CF₃)₂CF]₂ CFCF₂ CF₃ which is assumed to be an inactive component

EXAMPLE 72 [(CF₃)₂ CF]₂ C═CFCF₃ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 2.0 ml [(CF₃)₂ CF]₂ C═CFCF₃ *, dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane), wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 116 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at 10 g/min at 350° C. (estimated residencetime 1.2 min) and 96.5 MPa for 112 minutes. After vacuum pump drying atroom temperature, this gave 34.4 g of poly (HFP/TFE) for a productivityof 1.8 kg/L/hr. The polymer gave a highly viscous, hazy solution inFC-75. Fluorine NMR in the melt at 225° C. found 52 wt % HFP/48 wt % TFEwith 2.5% of the HFP methines as triads. Inherent viscosity in FC-75 at25° C. was 0.806. Roughly 16 g of polymer were made per gram ofinitiator.

EXAMPLE 73 C₂ F₅ SO₂ C₂ F₅ Initiation

A. Initiation at 275° C.: The 10 cc shaken autoclave was set up as inExample 1. Instead of using NF₃ as initiator, a solution of 0.5 ml C₂ F₅SO₂ C₂ F₅ (˜0.95 g) dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to 96.5 MPa reservoir 2prior to the start of the run. A mix of this initiator with 111 g of TFEand 2000 g of HFP was run through the 10 ml agitated reactor at 12 g/minat 275° C. (estimated residence time 0.96 min) and 96.5 MPa for 150minutes. After vacuum pump drying at room temperature, this gave 47 g ofpoly (HFP/TFE) for a productivity of 1.9 kg/L/hr. At 1 g of polymer per5 ml of FC-75, an extremely viscous solution or near gel was obtained atroom temperature. Fluorine NMR in the melt at 340° C. found 45 wt %HFP/55 wt % TFE with 4.2% of the HFP methines as triads. GPC in FC-75 at80° C. found Mw=892,000, Mn=187,000, Mv=776,000. Inherent viscosity inFC-75 at 25° C. was 0.931. Roughly 58 g of polymer were made per gram ofC₂ F₅ SO₂ C₂ F₅ initiator.

B. Initiation at 350° C.: The 10 cc shaken autoclave was set up as inExample 1. Instead of using NF₃ as initiator, a solution of 0.5 ml C₂ F₅SO₂ C₂ F₅ (˜0.95 g) dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to 96.5 MPa reservoir 2prior to the start of the run. A mix of this initiator with 112 g of TFEand 2000 g of HFP was run through the 10 ml agitated reactor at 12 g/minat 350° C. (estimated residence time 0.96 min) and 96.5 MPa for 135minutes. After vacuum pump drying at room temperature, this gave 97.6 gof poly (HFP/TFE) for a productivity of 4.3 kg/L/hr. One gram of polymergave an attractive, clear solution in 5 ml of FC-75 at room temperature.Fluorine NMR in the melt at 340° C. found 55 wt % HFP/45 wt % TFE. GPCin FC-75 at 80° C. found Mw=374,000, Mn=152,000, Mv=326,000. Inherentviscosity in FC-75 at 25° C. was 0.408. Roughly 130 g of polymer weremade per gram of C₂ F₅ SO₂ C₂ F₅ initiator.

C. Initiation at 400° C.: The 10 cc shaken autoclave was set up as inExample 1. Instead of using NF₃ as initiator, a solution of 1.03 g C₂ F₅SO₂ C₂ F₅ dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to 96.5 MPa reservoir 2prior to the start of the run. A mix of this initiator with 151 g of TFEand 2000 g of HFP was run through the 10 ml agitated reactor at ˜13-26g/min at 400° C. (estimated residence time ˜0.5 to 1 min) and 96.5 MPafor 85 minutes. Vacuum pump drying first at room temperature and thenfor four hours at 150° C. gave 190 g of poly (HFP/TFE) for aproductivity of 15 kg/L/hr. Dissolving 1 g in 5 ml of FC-75 at roomtemperature gave a clear viscous solution, the most attractive solutionof any of the 400° C. samples. Fluorine NMR in the melt at 320° C. found58 wt % HFP/42 wt % TFE. GPC in FC-75 at 80° C. found Mw=307,000,Mn=111,000, Mv=274,000. Approximately 90 to 180 g of polymer were madeper gram of C₂ F₅ SO₂ C₂ F₅ initiator.

EXAMPLE 74 n-Perfluorohexyl Iodide Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.5 ml n-perfluorohexyl iodide dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 113 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at 9 g/min at 350° C. (estimated residencetime 1.3 min) and 96.5 MPa for 90 minutes. After vacuum pump drying atroom temperature, this gave 39.6 g of poly (HFP/TFE) for a productivityof 2.6 kg/L/hr. One grain of polymer gave a hazy solution with a traceof particulates in 5 ml of FC-75 at room temperature. Fluorine NMR inthe melt at 340° C. found 56 wt % HFP/44 wt % TFE with 5% of the HFPmethines as triads. GPC in FC-75 at 80° C. found Mw=472,000, Mn=119,000,Mv=401,000. Inherent viscosity in FC-75 at 25° C. was 0.254. A NMRsample heated to 340° C. turned dark purple indicating the incorporationof iodine into the polymer although no iodine color was detected in amelt index sample heated only to 200° C. (melt index₂₀₀° C., 5 kg =4g/min). Roughly 100 g of polymer were made per gram of initiator.

EXAMPLE 75 2-Iodoheptafluoropropane Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.7 g 2-iodoheptafluoropropane dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to 96.5 MPa reservoir 2 prior to the start of the run. A mixof this initiator with 114 g of TFE and 2000 g of HFP was run throughthe 10 ml agitated reactor at ˜13 to 26 g/min at 350° C. (estimatedresidence time ˜0.5 to 1.0 min) and 96.5 MPa for 90 minutes. Aftervacuum pump drying at room temperature, this gave 102.8 g of poly(HFP/TFE) for a productivity of 6.8 kg/L/hr. The polymer was largelysoluble in FC-75, 1 g in 5 ml FC-75 giving a hazy solution with residualflocculent solid at room temperature. Fluorine NMR in the melt at 340°C. found 56 wt % HFP/44 wt % TFE. GPC in FC-75 at 80° C. foundMw=157,000, Mn=48,400, Mv=135,000. Roughly 130 to 270 g of polymer wereformed per gram of 2-iodoheptafluoropropane initiator.

EXAMPLE 76 1,6-Diiodododecafluorohexane Initiation

A. 1X I(CF₂)₆ I: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, a solution of 1.28 g1,6-diiodododecafluorohexane dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to 96.5 MPa reservoir 2prior to the start of the run. A mix of this initiator with 224 g of TFEand 4000 g of HFP was run through the 10 ml agitated reactor at 12.5g/min at 350° C. (estimated residence time 1.0 min) and 96.5 MPa for 238minutes. After vacuum pump drying at room temperature, this gave 180 gof poly (HFP/TFE) for a productivity of 4.5 kg/L/hr. One gram of polymergave a solution with trace flocculent solids in 5 ml FC-75 at roomtemperature. Fluorine NMR in the melt at 320° C. found 59 wt % HFP/41 wt% TFE, the polymer sample turning pink with heating to 320° C. GPC inFC-75 at 80° C. found Mw=221,000, Mn=76,500, Mv=190,000. Roughly 200 gof polymer were formed per gram of 1,6-diiodododecafluorohexaneinitiator.

B. 10X I(CF₂)₆ I: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, 12.8 g 1,6-diiodododecafluorohexanewas introduced to 96.5 MPa reservoir 2 prior to the start of the run. Amix of this initiator with 222 g of TFE and 4000 g of HFP was runthrough the 10 ml agitated reactor at 36.5 g/min at 350° C. (estimatedresidence time 0.3 min) and 96.5 MPa for 105 minutes. Vacuum drying atroom temperature gave 134 g of poly (HFP/TFE) for a productivity of 7.6kg/L/hr. The polymer was soluble in FC-75, 1 g in 5 ml FC-75 giving ahazy solution with residual flocculent solid at room temperature.Fluorine NMR in the melt at 320° C. found 47 wt % HFP/53 wt % TFE, thepolymer sample turning deep purple with heating to 320° C. GPC in FC-75at 80° C. found Mw=94,800, Mn=20,300, Mv=66,700. Roughly 11 g of polymerwere formed per gram of 1,6-diiodododecafluorohexane initiator.

EXAMPLE 77 (C₄ F₉)₂ NF Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.5 ml (C₄ F₉)₂ NF dissolved in 2.0 mlof HFP cyclic dimer (perfluorodimethylcyclobutane) was introduced to96.5 MPa reservoir 2 prior to the start of the run. A mix of thisinitiator with 114 g of TFE and 2000 g of HFP was run through the 10 mlagitated reactor at 11 g/min at 350° C. (estimated residence time 1.0min) and 96.5 MPa for 115 minutes. After vacuum pump drying at roomtemperature, this gave 80.2 g of poly (HFP/TFE) for a productivity of4.2 kg/L/hr. One gram of polymer gave a hazy solution in 5 ml of FC-75at room temperature. Fluorine NMR in the melt at 320° C. found 57 wt %HFP/43 wt % TFE with 8.0% of the HFP methines as triads. GPC in FC-75found Mw=426,000, Mn=187,000, Mv=378,000. Inherent viscosity in FC-75 at25° C. was 0.380. Roughly 150 g of polymer were made per gram of (C₄F₉)₂ NF initiator.

When the polymer sample prepared here was heated at 10° C./min under N₂,about 7% weight loss occurred between 50 and 130° C. Weight then stayedsteady up until 320° C., at which point another ˜10% weight lossoccurred between ˜320 and 420° C. and finally ˜70% by 500° C., theprocesses between 320 and 500° C. presumably reflecting breaking of thepolymer backbone. This onset of backbone degradation at 320° C. is oneof the reasons we are surprised that attractive high MW polymer can bemade up to at least 400° C. The volatiles lost between 50 and 130° C.were identified as largely perfluoromethylcyclobutane by infraredcomparison to a genuine sample. If one wishes, virtually all of theperfluoromethylcyclobutane can be removed from a ˜1:1 HFP copolymersample by heating for several hours at 150° C. in a vacuum oven. Theamount of perfluoromethylcyclobutane retained by polymer samples willreflect polymerization conditions (to what extent polymerizationconditions favor the cycloaddition of TFE to HFP as a side reaction) aswell as the conditions under which the polymer sample is collected(pressure, temperature, etc.). Once in the polymer sample,pefluoromethylcyclobutane is retained quite tightly. For many purposes,however, perfluoromethylcyclobutane can be considered an innocuousinert.

EXAMPLE 78 NF₃ Initiation

A. About 12:1 HFP: TFE, 1X NF₃ : The 10 cc shaken autoclave was set upas in Example 1. The 25 ml loop (1) off the feed line to reservoir (2)was pressured to 345 kPa (gauge) with nitrogen trifluoride at ambienttemperature. A mix of this initiator with 218 g of TFE and 4000 g of HFPwas run through the 10 ml agitated reactor at 13 g/min at 350° C.(estimated residence time 0.9 min) and 96.5 MPa for 288 minutes. Aftervacuum pump drying at room temperature, this gave ˜302 g of poly(HFP/TFE) for a productivity of ˜6 kg/L/hr. One gram of polymer gave asolution with trace haze in 5 ml of FC-75 at room temperature. FluorineNMR in the melt at 320° C. found 58 wt % HFP/42 wt % TFE with 8% of theHFP methines as triads. GPC in FC-75 at 80° C. found Mw=235,000,Mn=74,200, Mv=198,000. Inherent viscosity in FC-75 at 25° C. was 0.274.Roughly 1030 g of polymer were made per gram of NF₃ initiator.

B. About 12:1 HFP: TFE, 9X NF₃ : The polymerization above was repeatedincreasing the concentration of NF₃ initiator ˜9 times while keepingother variables roughly the same. The 10 cc shaken autoclave was set upas in Example 1. The 25 ml loop (1) off the feed line to reservoir (2)was pressured to 3.13 MPa (gauge) with nitrogen trifluoride at ambienttemperature. A mix of this initiator with 228 g of TFE and 4000 g of HFPwas run through the 10 ml agitated reactor at 11 to 22 g/min at 350° C.(estimated residence time ˜0.5 to 1.1 min) and 96.5 MPa for 315 minutes.After vacuum pump drying at room temperature, this gave 384 g ofpoly(HFP/TFE) for a productivity of 7.3 kg/L/hr. One gram of polymergave a clear solution in 5 ml of FC-75 at room temperature. Fluorine NMRin the melt at 340° C. found 56 wt % HFP/44 wt % TFE with 10% of the HFPmethines as triads. GPC in FC-75 at 80° C. found Mw=212,000, Mn=81,000,Mv=182,000. Inherent viscosity in FC-75 at 25° C. was 0.181.Approximately 100 to 200 g of polymer were made per gram of NF₃initiator.

C. About 16:1 HFP: TFE, 2X NF₃ : The 10 cc shaken autoclave was set upas in Example 1. The 25 ml loop (1) off the feed line to reservoir (2)was pressured to 758 kPa (gauge) with nitrogen trifluoride at ambienttemperature. A mix of this initiator with 169 g of TFE and 4000 g of HFPwas run through the 10 ml agitated reactor at 13 g/min at 350° C.(estimated residence time 0.9 min) and 96.5 MPa for 252 minutes. Aftervacuum pump drying at room temperature, this gave ˜215 g of poly(HEP/TFE) for a productivity of ˜5 kg/L/hr. One gram of polymer gave aclear solution in 5 ml FC-75 at room temperature. Fluorine NMR in themelt at 320° C. found 58 wt % HFP/42 wt % TFE with 9% of the HFPmethines as triads. Inherent viscosity in FC-75 at 25° C. was 0.216.Roughly 440 grams of polymer were made per gram of initiator.

D. About 24:1 HFP: TFE, 2X NF₃ : The 10 cc shaken autoclave was set upas in Example 1. The 25 ml loop (1) off the feed line to reservoir (2)was pressured to 758 kPa (gauge) with nitrogen trifluoride at ambienttemperature. A mix of this initiator with 112 g of TFE and 4000 g of HFPwas run through the 10 ml agitated reactor at 12 g/min at 350° C.(estimated residence time 1.0 min) and 96.5 MPa for 300 minutes. Vacuumpump drying at room temperature and then overnight under vacuum at 150°C. gave 140 g of poly (HFP/TFE) for a productivity of 3 kg/L/hr. Onegram of polymer gave a clear solution in 5 ml of FC-75 at roomtemperature. Fluorine NMR in the melt at 320° C. found 62 wt % HFP/38 wt% TFE with 7% of the HFP methines as triads. GPC in FC-75 at 80° C.found Mw=128,000, Mn=32,800, Mv=105,000. Inherent viscosity in FC-75 at25° C. was 0.187. Roughly 260 g of polymer were made per gram of NF₃initiator.

EXAMPLE 79 NF₃ Initiation

The 10 cc shaken autoclave was set up as in Example 1. The 25 ml loop(1) off the feed line to reservoir (2) was pressured to 345 kPa (gauge)with nitrogen trifluoride at ambient temperature. A mix of thisinitiator with 154 g of TFE and 2000 g of HFP was run through the 10 mlagitated reactor at 10 g/min at 400° C. (estimated residence time 1.2min) and 96.5 MPa for 55 minutes. Vacuum pump drying at room temperatureand then for 4 hours at 150° C. gave 53 g of poly (HFP/TFE) for aproductivity of 4.8 kg/L/hr. One gram polymer was soluble in 5 ml ofFC-75 at room temperature with residual haze. Fluorine NMR in the meltat 320° C. found 53 wt % HFP/47 wt % TFE with 4% of the HFP methines astriads. GPC in FC-75 at 80° C. found Mw=173,000, Mn=47,300, Mv=138,000.Roughly 620 g of polymer were made per gram of NF₃ initiator.

EXAMPLE 80 C₄ F₉ SSC₄ F₉ Initiation

A. At 350° C.: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, a solution of 0.5 ml C₄ F₉ SSC₄ F₉dissolved in 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane)was introduced to reservoir 2 prior to the start of the run. A mix ofthis initiator with 113 g of TFE and 2000 g of HFP was run through the10 ml agitated reactor at 11 g/min at 350° C. (estimated residence time1.0 min) and 96.5 MPa for 150 minutes. After vacuum pump drying at roomtemperature, this gave 50.23 g of poly (HFP/TFE) for a productivity of2.0 kg/L/hr. Consistent with its high molecular weight, 1 gram ofpolymer gave an extremely viscous, partial solution in 5 ml of FC-75 atroom temperature. Fluorine NMR in the melt at 340° C. found 50 wt %HFP/50 wt % TFE with 14.0% of the HFP methines as triads. GPC in FC-75at 80° C. found Mw=1,108,000, Mn=238,000, Mv=976,000. Inherent viscosityin FC-75 at 25° C. was 0.946. Roughly 70 g of polymer were made per gramof C₄ F₉ SSC₄ F₉ initiator.

B. At 400° C.: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, a solution of 0.5 ml C₄ F₉ SSC₄ F₉(0.89 g) dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to reservoir 2 prior tothe start of the run. A mix of this initiator with 151 g of TFE and 2000g of HFP was run through the 10 ml agitated reactor at ˜12.7 g /min at400° C. (estimated residence time ˜1.0 min) and 96.5 MPa for 85 minutes.After vacuum pump drying at room temperature and then for 4 hours undervacuum at 150° C., 185.9 g of poly (HFP/TFE) were obtained for aproductivity of 13.0 kg/L/hr. Mixing 1 g of polymer with 5 ml FC-75 atroom temperature gave a viscous solution with residual insolubles.Fluorine NMR in the melt at 320° C. found 54 wt % HFP/46 wt % TFE. GPCin FC-75 at 80° C. found Mw=361,000, Mn=113,000, Mv=306,000. Roughly 210g of polymer were made per gram of C₄ F₉ SSC₄ F₉ initiator.

EXAMPLE 81 (C₄ F₉)₂ NSCF₃ Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.5 ml (C₄ F₉)₂ NSCF₃ (0.92 g) dissolvedin 2.0 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) wasintroduced to reservoir 2 prior to the start of the run. A mix of thisinitiator with 80 g of TFE and 2200 g of HFP was run through the 10 mlagitated reactor at ˜11 g/min at 350° C. (estimated residence time 1.1min) and 96.5 MPa for 105 minutes. Vacuum pump drying at roomtemperature and then for 4 hours at 150° C. gave 97 g of poly (HFP/TFE)for a productivity of 5.5 kg/L/hr. One gram of polymer gave a viscoussolution with residual insolubles when mixed with 5 ml of FC-75 at roomtemperature. Fluorine NMR in the melt at 320° C. found 55 wt % HFP/45 wt% TFE. GPC in FC-75 at 80° C. found Mw=391,000, Mn=116,000, Mv=332,000.Roughly 210 g of polymer were made per gram of (C₄ F₉)₂ NSCF₃ initiator.

EXAMPLE 82 (C₄ F₉)₃ N Initiation

A. At 350° C.: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, a solution of 0.5 ml (C₄ F₉)₃ N (0.94g) dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to reservoir 2 prior tothe start of the run. A mix of this initiator with 117 g of TFE and 2000g of HFP was run through the 10 ml agitated reactor at 11 g/min at 350°C. (estimated residence time 1.0 min) and 96.5 MPa for 117 minutes.After vacuum pump drying at room temperature, this gave 25 g of poly(HFP/TFE) for a productivity of 1.3 kg/L/hr. The polymer gave anextremely viscous solution or gel in FC-75. GPC in FC-75 at 80° C. foundMw=1,238,000, Mn=153,000, Mv=1,087,000. Inherent viscosity in FC-75 at25° C. was 1.375. Roughly 26 g of polymer were made per gram of (C₄ F₉)₃N initiator.

B. At 400° C.: The 10 cc shaken autoclave was set up as in Example 1.Instead of using NF₃ as initiator, a solution of 0.5 ml (C₄ F₉)₃ N (0.94g) dissolved in 2.0 ml of HFP cyclic dimer(perfluorodimethylcyclobutane) was introduced to reservoir 2 prior tothe start of the run. A mix of this initiator with 157 g of TFE and 2000g of HFP was run through the 10 ml agitated reactor at 13 g/min at 400°C. (estimated residence time 0.9 min) and 96.5 MPa for 124 minutes.After vacuum pump drying at room temperature and then for ˜15 hoursunder vacuum at 150° C., 120.0 g of poly (HFP/TFE) were obtained for aproductivity of 5.8 kg/L/hr. Mixing 1 g of polymer with 5 ml of FC-75 atroom temperature gave a solution with residual insolubles. Fluorine NMRin the melt at 320° C. found 55 wt % HFP/45 wt % TFE. GPC in FC-75 at80° C. found Mw=289,000, Mn=78,300, Mv=238,000. Roughly 130 g of polymerwere made per gram of (C₄ F₉)₃ N initiator.

EXAMPLE 83 (C₄ F₉)₂ NF Initiation

The 10 cc shaken autoclave was set up as in Example 1. Instead of usingNF₃ as initiator, a solution of 0.8 ml (C₄ F₉)₂ NF (˜1.4 g) dissolved in5 ml of HFP cyclic dimer (perfluorodimethylcyclobutane) was introducedto reservoir 2 prior to the start of the run. A mix of this initiatorwith 223 g of TFE and 4000 g of HFP was run through the 10 ml agitatedreactor at 12 g /min at 275° C. (estimated residence time 1.1 min) and96.5 MPa for 315 minutes. After vacuum pump drying at room temperature,this gave 146 g of poly (HFP/TFE) for a productivity of 2.8 kg/L/hr. Atroom temperature 1 g of polymer dissolved in 5 ml of FC-75. Fluorine NMRin the melt at 340° C. found 47 wt % HFP/53 wt % TFE with 7.4% of theHFP methines as triads. GPC in FC-75 at 80° C. found Mw=603,000,Mn=226,000, Mv=546,000. Inherent viscosity in FC-75 at 25° C. was 0.679.Roughly 110 g of polymer were made per gram of (C₄ F₉)₂ NF initiator.

EXAMPLE 84 No Added Initiator

A. At 350° C.: The 10 cc shaken autoclave was set up as in Example 1. Noinitiator at all was added. A mix of 113 g of TFE and 2000 g of HFP wasrun through the 10 ml agitated reactor at 11 g/min at 350° C. (estimatedresidence time 1.0 min) and 96.5 MPa for 115 minutes. After vacuum pumpdrying at room temperature, this gave 17.2 g of poly (HFP/TFE) for aproductivity of 0.90 kg/L/hr. Rolling 1 g of polymer with 5 ml of FC-75at room temperature gave a hazy viscous solution. Fluorine NMR in themelt at 340° C. found 57 wt % HFP/43 wt % TFE. GPC in FC-75 at 80° C.found Mw=451,000, Mn=147,000, Mv=397,000.

B. At 400° C.: The 10 cc shaken autoclave was set up as in Example 1. Noinitiator at all was added. A mix of 154 g of TFE and 2000 g of HFP wasrun through the 10 ml agitated reactor at 12 g/min at 400° C. (estimatedresidence time 1.0 min) and 96.5 MPa for 110 minutes. After vacuum pumpdrying first at room temperature and then for four hours at 150° C.,77.9 g of poly (HFP/TFE) were obtained for a productivity of 4.2kg/L/hr. Rolling 1 g of polymer with 5 ml of FC-75 at room temperaturegave a hazy solution. Fluorine NMR in the melt at 320° C. found 57 wt %HFP/43 wt % TFE. GPC in FC-75 at 80° C. found Mw=262,000, Mn=69,900,Mv=208,000.

EXAMPLE 85 TFE/HFP Copolymerization in a Well Stirred Reactor

Three separate feed streams were converted to gases and metered into amixing vessel typically at 200-380 kPa. The mixture was then compressedin two stages to goal pressures. The compressed super-critical fluid wasfed to a preheater, held at 175 to 200° C. in these experiments, andthen into a stainless steel well-mixed reactor of 100 ml volume providedwith a mechanical stirrer running at 1100 rpm. The design of this feedsystem assures that the flows are uniform and well controlled, sincethey are all handled as gases and compressed together.

From the reactor the polymer solution flows through a reducing valve,which was also used to control reactor pressure at 96.5 MPa, and thenceinto an enclosed collection vessel at 156 kPa where the unreactedmonomers are allowed to evaporate. The evaporated monomers are condensedand collected in a separate system. Product was removed from thecollection vessel at the end of the run.

Typical example conditions are shown in the following table which alsoshows the properties of the resulting product.

    ______________________________________                                                 Units Run A     Run B     Run C                                      ______________________________________                                        Feed 1: (100% HPF)                                                                       Kg/hr   4.7       5.03    3.84                                       Feed 2:                                                                       Wt. % NF.sub.3 in HFP Wt. % 1.32 2.49 0.87                                    Rate Kg/hr 0.045 0.049 0.022                                                  Feed 3: (100% TFE) Kg/hr 0.21 0.20 0.26                                       Mixer Pressure kPa 255 276 200                                                Preheater ° C. 175 200 190                                             Temperature                                                                   Reactor ° C. 267 275 284                                               Temperature                                                                   Polymerization MPa 96.5 96.5 41.3-55.1                                        Reactor Pressure                                                              Production rate gm/hr 168 196 248                                             Product properties:                                                           Wt percent HFP % 54.7 58.9 50.7                                               Molecular  113,000 71,600 140,000                                             weight Mn                                                                     Molecular  325,000 170,000 371,000                                            weight Mw                                                                     Mw/Mn  2.87 2.37 2.64                                                         Calculated TFE % 36.2 40.3 43.6                                               conversion                                                                  ______________________________________                                    

EXAMPLE 86 CF₃ CF₂ CF₂ C(CF₃)₂ NF₂

A: A 2 liter r.b. flask with a stirring bar was charged with 75 g ofdry, ball-milled KF in a glove box. The flask was transferred to a hood,swept with nitrogen, and 1 liter of 4A molecular sieve drieddimethylformamide added with stirring. The contents of the flask werechilled to -12° C. and the addition of phenyldiazonium tetrafluoroboratewas begun. Soon into the addition the contents of the flask were furtherchilled to -37° C. and phenyldiazonium tetrafluoroborate additioncontinued, a total of 282.9 g being added.

With the temperature at -35 to -40° C., 325.3 g of (CF₃)₂ C═CFCF₂ CF₃were added in a trickle, then 27.2 g of dry KF, and finally another119.6 g of (CF₃)₂ C═CFCF₂ CF₃. As the last of the (CF₃)₂ C═CFCF₂ CF₃ wasrun in, temperature increased to -31° C. and foaming increased. Thereaction mixture was chilled to and held at -38° C. for an hour.Temperature was allowed then to gradually rise to room temperature. Thereaction mixture was stirred overnight at room temperature undernitrogen. The solids were filtered off and washed with ether. Thefiltrate was taken up in about 2 liters of ether, washed with water, 5Xwith 5% NaOH, 4X with 5% HCl, each aqueous wash back-washed with 1 literof ether. The ether layer was washed with saturated sodium chloride,dried over CaCl₂, and concentrated on a rotary evaporator. This gave283.6 g of crude dark red oil. This oil was dissolved in 500 g oftrifluoroacetic acid. Reduction was quite slow taking the addition of 54g amalgamated zinc, 44 g of amalgamated zinc four days later, 300 gtrifluoroacetic acid and 40 g amalgamated zinc about 23 days later, andthen an additional 15 day wait. The reaction mixture was worked up byadding 1 liter of distilled water and steam distilling directly out ofthe flask. Steam distillation accompanied by foaming gave 152.7 g ofcrude CF₃ CF₂ CF₂ C(CF₃)₂ NH₂ using a Dean-Stark trap for collection.Three such batches (totaling ˜360 g) ranging in &C purity from 79 to 96%were combined and added slowly to 50 ml Et₂ NH mixed with 100 ml 40%aqueous KOH (exotherm, slow addition). After stirring overnight, thereaction mixture was poured into water, washed several times with 5%HCl, and dried. Attempted distillation at this point gave fumes anddiscoloration and was discontinued. The reaction mixture was added to asolution made by dissolving 133 g of 85% KOH in 150 ml water and 500 mlethanol. This mixture was stirred overnight and then refluxed over thenext night. Water was added to nearly fill the 2 liter reaction flaskand then the contents steam distilled. This distillate was washed withwater and the lower layer, 284.8 g, then dried over CaCl₂. The fluorineNMR was very clean while GC showed a short retention time impurity withan area of 8.7%. This CF₃ CF₂ CF₂ C(CF₃)₂ NH₂ was used in step B below.

B: A 60 ml Teflon® bottle was loaded with 9.62 g of CF₃ CF₂ CF₂ C(CF₃)₂NH₂. Over a period of 4.55 hr, 1726 ml of F₂ gas was passed into thebottle at atmospheric pressure and room temperature while stirring thecontents gently. The reaction mixture was let stand overnight at roomtemperature. A pipette was used to withdraw 8.33 g of light yellow fluidfrom the Teflon® bottle. Fluorine NMR was consistent with quantitativeconversion to the desired CF₃ CF₂ CF₂ C(CF₃)₂ NF₂ : +36.0 ppm (1.9 F),-62.3 ppm (6.0 F), -81.0 ppm (3.05 F), -109.2 ppm (1.9 F), -123.3 ppm(2.0 F). No other adsorptions were visible in the fluorine NMR, yield78%. In a similar, larger scale run, a center cut of colorlessdistillate was taken off a little NaF (bp₇₆₀ =84-88° C.).

    ______________________________________                                        Calc. for C.sub.6 F.sub.13 NF.sub.2 :                                                      19.42C      76.80F  3.78N                                          Found: 19.35C 76.93F 3.71N                                                  ______________________________________                                    

EXAMPLE 87 (C₄ F₉)₂ NSCF₃

A 100 ml flask was charged with C₄ F₉ N═CFC₃ F₇ (5.0 g 11.5 mmol), CsF(2.3 g, 15 mmol), and 10 ml of diethyl ether under a N₂ atmosphere.After stirring for 3 hours at room temperature, the mixture was cooledto ˜5° C. by an ice-water bath and CF₃ SCl (excess) added via a dryice-acetone condenser until a slight yellow color was observed in themixture. The resulting mixture was stirred at room temperature for oneday. Then the mixture was filtered, the filtrate partially distilled toremove ether, and the residue bulb-to-bulb distilled at reduced pressureto afford 4.8 g (75%) of colorless liquid, a small amount of which whenheated in a melting point capillary showed the initiation of boiling at˜145° C. ¹⁹ F NMR was consistent with the desired product (C₄ F₉)₂ NSCF₃: -50.1 (m, 3F), -81.4 (t, J=10 Hz, 6F), -86.0 (AB q, J=233 Hz, 4F),-121.0 (AB q, J=290 Hz, 4F), -126.9 (t, J=15 Hz, 4F).

EXAMPLES 88-118 Other Monomers in High Temperature Polymerization

Experimental

New monomer combinations are described in Examples 88-118 below.Polymerizations were run in a semicontinuous fashion using the equipmentand general methods described in Example 1. Weights of TFE added to themixing reservoir were calculated the same way as in Examples 66 and 84.In cases where an NMR analysis of polymer composition was not available,elemental analysis was often performed assuming a 1:1 HFP:TFE molarratio for purposes of calculation. At high levels of incorporation andhigh temperatures, those termonomers with chain transferring groupsoften gave greases and oils rather than solid polymer. This includesmethyl vinyl ether, propylene, isobutylene, and CH₃ CH₂ CH₂ CH₂ OCF═CF₂.

Compositions for many of the TFE/HFP copolymers were determined from ¹⁹F spectra taken either on polymer melts at 300 to 340° C. or onsolutions in hexafluorobenzene at 80° C. Integration of the CF peaks at-174 ppm to -185 ppm was used to determine HFP content, and the CF₂absorptions at -100 ppm to -125 ppm, corrected for comonomercontributions, for the TFE content. The termonomer content wasdetermined from the integrated intensities of the relevant signals: CF₃CF₂ CF₂ CF₂ CH═CH₂ (Example 97) from the signal at -82.5 ppm, CF₂═CFOCF₂ (CF₃)CF)CF₂ CF₂ SO₂ F and CF₂ ═CFCF₂ OCF₂ CF₂ SO₂ F (Examples94A and 93) from the signal at +46.2 ppm, CH₂ ═CHOCOCF₃ (Example 96)from the signal at -77.5 ppm, CF₂ ═CFOCF₂ (CF₃)CF)CF₂ CF₂ SO₂ F in themelt (Example 94B) using various -OCF absorptions around -75 to -83 and-136 to -140 ppm, CF₂ ═CFCF₂ CN (Example 92) from the signal at -107ppm, CTFE (Example 91A) from the signals at -129 ppm -134 ppm, CF₃CH═CH₂ from the CF₃ CH signal at -67 ppm, perfluorocyclobutene bydifference between the observed excess CF's around -175 to -185 ppmcompared to what expected from HFP alone (Example 106),perfluorocyclopentene (Example 107) same as the perfluorocyclobutene,CF₂ ═C(CF₃)COF from the --COF resonance at about 20 ppm (Example 109),trifluoroethylene from the --CFH-- resonance at -199 ppm (Example 110),perfluoro-2-methylene-4-methyl-1,3-dioxolane from the resonances for the--OCF₂ and the --CF₃ at -80 to -82 ppm (Example 111).

Composition of polymers containing VF2 as the third monomer (Example 88to 90) were determined from both the ¹⁹ F spectrum and a ¹ H spectrumtaken on a sample of the polymer into which an internal standard,containing both fluorine and protons, had been added. The VF2 ¹ H signalat 2.2 ppm was ratioed to the internal standard signals, converted intoan absolute amount of VF2 which was subtracted from a weighed amount ofthe polymer to give the amount of polymer which was not VF2. Polymerscontaining both TFE and HFP along with VF2 determined the TFE and HFP inthe way mentioned above.

The composition of polymers containing ethylene as a third monomer(Example 98) were determined from both the ¹⁹ F and ¹³ C spectra takenon solutions in hexafluorobenzene. The ¹⁹ F spectrum was used todetermine the ratio of the HFP to TFE. The ¹³ C spectrum was used todetermine the integrated intensities of the CF₂ signals at 106 ppm-126ppm, the CF signals at 91 ppm-99 ppm, and the CH₂ signals at 20 ppm-28ppm.

The composition of the IFP/TFE/CF₃ CF═CH₂ terpolymer was determined by¹³ C NMF using the CH₂ carbon from 30 and 32 ppm for CF₃ CF═CH₂, the CFcarbon at 98 to 100 ppm for CF₃ CF═CF₂ after subtraction of the CFcontributed by tetrafluoropropene, and the CF₂ carbon from 110 to 132ppm for TFE after subtraction of CF₃ and CF₂ carbons contributed byhexafluoropropene and tetrafluoropropene (Example 101).

EXAMPLE 88 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 4000 g of HFP,220 g TFE, 3 g vinylidene fluoride, and about 1.2 g of NF₃ was made in96.5 MPa reservoir (2). About 3548 g of this mixture were run throughthe 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 275 minuteperiod. Drying the product under vacuum gave 177 g of white polymer.Analysis results are gathered below.

>1 g/5 ml of FC-75, clear solution at room temperature

Mw=299,000 by GPC in FC-75 at 80° C.

Mn=111,000 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.384

Melt index₁₈₅° C., 5 kg =0.7 g/min

Tg=28° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. @10° C./min under N₂

˜2 mole % VF2 by ¹⁹ F NMR in melt at 320° C.

˜39 mole % HFP by ¹⁹ F NMR in melt at 320° C.

˜59 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 3.8 kg/L/hr (32 lbs/gal/hr)

EXAMPLE 89 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 4000 g of HFP,164 g TFE, 40 g vinylidene fluoride, and about 1.2 g of NF₃ was made in96.5 MPa reservoir (2). About 3302 g of this mixture were run throughthe 10 ml shaken autoclave at 275° C. and 96.5 MPa over a 185 minuteperiod. Drying the product under vacuum gave 180 g of white polymer.Analysis results are gathered below.

Little or partial solubility at 1 g/5 ml FC-75, Freon® 113, or acetoneat r.t.

Mw=122,000 by GPC in FC-75 at 80° C.

Mn=38,300 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.247 (cloudy solution)

Melt index₁₈₅° C., 5 kg =1 g/min

Tg=2° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 410° C. @10° C./min under N₂

˜29 mole % VF2 by ¹⁹ F NMR in melt at 300° C.

˜39 mole % HFP by ¹⁹ F NMR in melt at 300° C.

˜32 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 5.8 kg/L/hr (49 lbs/gal/hr)

EXAMPLE 90 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/VF2

The same set up was used as in Example 1. A mixture of 2000 g of HFP, 80g vinylidene fluoride, and about 0.6 g of NF₃ was made in 96.5 MPareservoir (2). About 1656 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 139 minute period.Drying the product under vacuum gave 105 g of white polymer. Analysisresults are gathered below.

0.1 g/l ml solubility in Freon® 113 or acetone at r.t.

Inherent Viscosity in Freon® 113 at 25° C.=0.044

Tg=-5° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 190° C. @10° C./min under N₂

˜59 mole % VF2 by ¹⁹ F NMR in melt at 300° C.

˜41 mole % HFP by ¹⁹ F NMR in melt at 300° C.

Productivity 4.5 kg/L/hr (38 lbs/gal/hr)

EXAMPLE 91 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CTFE

A. ˜124:9.2:1 HFP:TFE:CTFE: The same set up was used as in Example 1. Amixture of 4000 g of HFP, 197 g TFE, 25 g chlorotrifluoroethylene, andabout 1.2 g of NF₃ was made in 96.5 MPa reservoir (2). About 4057 g ofthis mixture were run through the 10 ml shaken autoclave at 250° C. and96.5 MPa over a 266 minute period. Drying the product under vacuum gave120 g of white polymer. Analysis results are gathered below.

1 g/5 ml soluble in FC-75 at r.t. with a trace of flocculent residue

Mw=171,000 by GPC in FC-75 at 80° C.

Mn=65,300 by GPC in FC-75 at 80° C.

Tg=30° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature, 410° C. @10° C./min under N₂

2.9 mole % CTFE by ¹⁹ F NMR in melt at 320° C.

40.6 mole % HFP by ¹⁹ F NMR in melt at 320° C.

56.5 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 2.7 kg/L/hr (22 lbs/gal/hr)

B. ˜15:1.2:1 HFP:TFE:CTFE: The same setup was used as in Example 1. Amixture of 2000 g of HFP, 108 g TFE, 100 g chlorotrifluoroethylene, andabout 0.6 g of NF₃ was made in 96.5 MPa reservoir (2). About 1913 g ofthis mixture were run through the 10 ml shaken autoclave at 250° C. and96.5 MPa over a 140 minute period. Drying the product under vacuum gave107 g of white polymer. Analysis results are gathered below.

1 g/5 ml soluble in FC-75 at r.t., hazy flocculent residue

Mw=39,100 by GPC in FC-75 at 80° C.

Mn=15,300 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =8 g/min

Tg=26° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature, 390° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min under N₂

19 mole % CTFE by ¹⁹ F NMR in melt at 320° C.

27 mole % HFP by ¹⁹ F NMR in melt at 320° C.

54 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 4.6 kg/L/hr (38 lbs/gal/hr)

EXAMPLE 92

Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/NCCF₂ CF═CF₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,114 g TFE, 68 g NCCF₂ CF═CF₂, and about 1.2 g of NF₃ was made in 96.5MPa reservoir (2). About 1912 g of this mixture were run through the 10ml shaken autoclave at 275° C. and 96.5 MPa over a 175 minute period.Drying the product under vacuum gave 32 g of white polymer. Analysisresults are gathered below.

1 g soluble 5 ml FC-75 at r.t. with a bit of residual flocculent solids

Mw=58,900 by GPC in FC-75 at 80° C.

Mn=24,800 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.119

Melt index₁₀₀° C., 5 kg =2.4 g/min

Tg=25° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature, 410° C. @10° C./min under N₂

˜0.6 mole % NCCF₂ CF═CF₂ by ¹⁹ F NMR, hexafluorobenzene, 80° C.

˜37 mole % HFP by ¹⁹ F NMR, hexafluorobenzene solution, 80° C.

˜62 mole % TFE by ¹⁹ F NMR, hexafluorobenzene solution, 80° C.

Productivity 1.1 kg/L/hr (9 lbs/gal/hr)

EXAMPLE 93 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/FSO₂ CF₂ CF₂ OCF₂ CF═CF₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,114 g TFE, 84 g FSO₂ CF₂ CF₂ OCF₂ CF═CF₂, and about 1.2 g of NF₃ wasmade in 96.5 MPa reservoir (2). About 1125 g of this mixture were runthrough the 10 ml shaken autoclave at 275° C. and 96.5 MPa over a 115minute period. Drying the product under vacuum gave 61.5 g of whitepolymer. Of this a 10.9 g sample was dried for another 4 hours at 150°C. in a vacuum oven, giving 10.4 g fused solid with the followinganalyses. Analysis results are gathered below.

1 g soluble 5 ml FC-75 at r.t. with a bit of residual flocculent solids

Mw=142,000 by GPC in FC-75 at 80° C.

Mn=55,800 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.190

Melt index₂₀₀° C., 5 kg =4 g/min

Tg=26° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 430° C. @10° C./min under N₂

˜0.25 mole % FSO₂ CF₂ CF₂ OCF₂ CF═CF₂ by ¹⁹ F NMR in melt at 150° C.

˜37 mole % HFP by ¹⁹ F NMR in melt at 150° C.

˜63 mole % TFE by ¹⁹ F NMR in melt at 150° C.

Productivity 3.0 kg/L/hr (25 lbs/gal/hr)

EXAMPLE 94 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/FSO₂ CF₂ CF₂ OCF(CF₃)CF₂ OCF═CF₂ (PSEPVE)

A. ˜240:20:1 HFP:TFE:PSEPVE. The same set up was used as in Example 1. Amixture of 4000 g of HFP, 221 g TFE, 30 mL FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂, and about 1.2 g of NF₃ was made in 96.5 MPa reservoir (2).About 1639 g of this mixture were run through the 10 ml shaken autoclaveat 250° C. and 96.5 MPa over a 184 minute period. The polymer was driedunder vacuum first at room temperature and then overnight at 150° C.giving 62 g of fused sheet. Analysis results are gathered below.

1 g soluble 5 ml FC-75 at r.t. with a trace of haze

Mw=77,600 by GPC in FC-75 at 80° C.

Mn=37,300 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.128

Tg=14° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 380° C. @10° C./min under N₂

˜0.7 mole % FSO₂ CF₂ CF₂ OCF(CF₃)CF₂ OCF═CF₂ by ¹⁹ F NMR inhexafluorobenzene solution at 80° C.

˜37 mole % HFP by ¹⁹ F NMR in hexafluorobenzene solution at 80° C.

˜61 mole % TFE by ¹⁹ F NMR in hexafluorobenzene solution at 80° C.

˜1% FSO₂ CF₂ CF₂ OCF(CF₃)CF₂ OCF═CF₂ as free monomer by ¹⁹ F NMR inhexafluorobenzene solution at 80° C.

Productivity 2.0 kg/L/hr (17 lbs/gal/hr)

B. ˜240:30:1 HFP:TFE:PSEPVE. The same set up was used as in Example 1. Amixture of 2667 g of HIP, 224 g TFE, 33 g FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂, and about 1.2 g of NF₃ was made in 96.5 MPa reservoir (2).About 2527 g of this mixture were run through the 10 ml shaken autoclaveat 250° C. and 96.5 MPa over a 215 minute period. The polymer was driedunder vacuum first at room temperature and then for 4 hours at 150° C.giving 232.9 g. TGA found that about 5 wt % of PSEPVE was still retainedby the polymer coming off at about 130-170° C. The remaining 221.7 gsample of polymer was further dried for 4 hours at 200° C. in a vacuumoven, giving 200.3 g of flexible orange, clear polymer. Analysis resultsare gathered below.

1 g partially soluble in 5 ml FC-75 at r.t.

Mw=61,600 by GPC in FC-75 at 80° C.

Mn=25,300 by GPC in FC-75 at 80° C.

Tg=15° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 390° C. @10° C./min under N₂

Tm, none detected by DSC 10° C./min, N₂, second heat

0.6 mole % FSO₂ CF₂ CF₂ OCF(CF₃)CF₂ OCF═CF₂ by ¹⁹ F NMR 320° C.

35.2 mole % HFP by ¹⁹ F NMR in melt at 320° C.

64.2 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 5.9 kg/L/hr (49 lbs/gal/hr)

EXAMPLE 95

Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/Perfluoro-2-Methyl-2,3-dihydro-1,4-dioxin (PMDD)

The same set up was used as in Example 1. A mixture of 1000 g of HFP, 62g TFE, 24.7 g perfluoro-2-Methyl-2,3-dihydrol, 4-dioxin, and about 0.6 gof NF₃ was made in 96.5 MPa reservoir (2). About 650 g of this mixturewere run through the 10 ml shaken autoclave at 275° C. and 96.5 MPa overa 54 minute period. The polymer was dried under vacuum at roomtemperature, 53.5 g.

1 g largely soluble 5 ml FC-75 at r.t. with a residue of flocculentsolid

Mw=53,600 by GPC in FC-75 at 80° C.

Mn=25,100 by GPC in FC-75 at 80° C.

Inherent Viscosity in FC-75 at 25° C.=0.092

Tg=30° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

˜0.5 mole % perfluoro(5-methyl-2,3-dihydro-1,4-dioxin) by ¹⁹ F NMR inmelt at 300° C.

˜45 mole % HFP by ¹⁹ F NMR in melt at 300° C.

˜55 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 5.9 kg/L/hr (49 lbs/gal/hr)

EXAMPLE 96 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHO(C═O)CF₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP,113 g TFE, 10 ml (12 g) vinyl trifluoroacetate, and ˜1.2 g of NF₃ wasmade in 96.5 MPa reservoir (2). About 1739 g of this mixture were runthrough the 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 152minute period. Drying the product under vacuum gave 105.3 g of whitepolymer, a 10.32 g sample of which was dried further for 4 hours at 150°C. under vacuum, giving 9.9 g of colorless polymer. Results for the ovendried 9.9 g sample are gathered below.

1 g/5 ml FC-75 at r.t., hazy solution, trace insolubles

Mw=78,900 by GPC in FC-75 at 80° C.

Mn=23,500 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =8 g/min

Tg=26° C. (second heat) by DSC 10° C./min under N₂

10% weight loss temperature 380° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

˜5 mole % CH₂ ═CHO(C═O)CF₃ by ¹⁹ F NMR in melt

˜41 mole % HFP by ¹⁹ F NMR in melt

˜54 mole % TFE by ¹⁹ F NMR in melt

Productivity 4.0 kg/L/hr (33 lbs/gal/hr)

EXAMPLE 97

Continuous Polymerization in 10 ml Autoclave with Agitation HFP/TFE/CH₂═CHCF₂ CF₂ CF₂ CF₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP,114 g TFE, 10 ml (14.4 g) perfluorobutylethylene, and ˜1.2 g of NF₃ wasmade in 96.5 MPa reservoir (2). About 1777 g of this mixture were runthrough the 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 135minute period. Drying the product under vacuum gave 51.8 g of whitepolymer, a 10.13 g sample of which was dried further for 4 hours at 150°C. under vacuum, giving 8.75 g of colorless polymer. Analysis resultsfor the oven dried 8.75 g sample are gathered below.

1 g/5 ml FC-75 at r.t., hazy solution, trace insolubles

Mw=53,000 by GPC in FC-75 at 80° C.

Mn=22,700 by GPC in FC-75 at 80° C.

Tg=17° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 390° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

4 mole % CF₃ CF₂ CF₂ CF₂ CH═CH₂ by ¹⁹ F NMR in melt at 320° C.

37 mole % HFP by ¹⁹ F NMR in melt at 320° C.

59 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 2.0 kg/L/hr (17 lbs/gal/hr)

EXAMPLE 98 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CH₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,113 g TFE, 8 g ethylene, and 1.2 g of NF₃ was made in 96.5 MPa reservoir(2). About 1533 g of this mixture were run through the 10 ml shakenautoclave at 250° C. and 96.5 MPa over a 143 minute period. Drying theproduct under vacuum gave 93.8 g of white polymer, a 10.78 g sample ofwhich was dried further for 4 hours at 150° C. under vacuum, giving10.45 g of colorless polymer. Results for the oven dried 10.45 g sampleare gathered below.

1 g/5 ml FC-75 at r.t., hazy, low viscosity solution

Mw=61,600 by GPC in FC-75 at 80° C.

Mn=19,000 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =2.7 g/min

Tg=23° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature, 380° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min under N₂

15.4 mole % ethylene by ¹³ C NMR in solution

40.2 mole % HFP by ¹³ C NMR in solution

44.4 mole % TFE by ¹³ C NMR in solution

Productivity 3.8 kg/L/hr (32 lbs/gal/hr)

EXAMPLE 99 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHCH₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP,114 g TFE, 8 g propylene, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1616 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 150 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 25.4 g ofpale yellow grease/oil.

1 g/5 to 10 ml FC-75 at r.t., clear solution

Mw=9,350 by GPC in FC-75 at 80° C.

Mn=4,220 by GPC in FC-75 at 80° C.

Tg=-23.7° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

TGA, 10° C./min., N₂, 10% weight loss at ˜150° C.

Productivity 1.0 kg/L/hr (8.4 lbs/gal/hr)

Elemental Analysis, Found: 1.68% H, 1.68% H Calc.:* (TFE).sub.˜1.28x(HFP).sub.˜1.28x (C₃ H₆)_(x) 1.67% H

EXAMPLE 100 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHCF₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP,105 g TFE, 10 g 3,3,3-trifluoropropene, and 1.2 g of NF₃ was made in96.5 MPa reservoir (2). About 1855 g of this mixture were run throughthe 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 160 minuteperiod. Drying the product under vacuum for 4 hours at 150° C. gave 98.8g of a fused mass that hardened on cooling.

1 g/5 to 10 ml FC-75 at r.t., clear solution

Mw=35,000 by GPC in FC-75 at 80° C.

Mn=13,800 by GPC in FC-75 at 80° C.

Tg=13° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 390° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

7 mole % CF₃ CH═CH₂ by ¹⁹ F NMR in melt at 320° C.

38 mole % HFP by ¹⁹ F NMR in melt at 320° C.

55 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 3.7 kg/L/hr (31 lbs/gal/hr)

EXAMPLE 101 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CFCF₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP,112 g TFE, 10 g 2,3,3,3-tetrafluoropropene, and ˜1.2 g of NF₃ was madein 96.5 MPa reservoir (2). About 1652 g of this mixture were run throughthe 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 151 minuteperiod. Drying the product for 4 hours at 150° C. under vacuum gave 74.8g of colorless polymer.

1 g/5 ml FC-75 at r.t., clear solution

Mw=42,900 by GPC in FC-75 at 80° C.

Mn=18,600 by GPC in FC-75 at 80° C.

Tg=17° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 380° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

8.6 mole % CF₃ CF═CH₂ ¹³ C NMR in hexafluorobenzene @60° C.

36.2 mole % HFP by ¹³ C NMR in hexafluorobenzene solution @60° C.

55.2 mole % TFE by ¹³ C NMR in hexafluorobenzene solution @60° C.

Productivity 3.0 kg/L/hr (25 lbs/gal/hr)

EXAMPLE 102 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═C(CH₃)₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,113 g TFE, 8 g isobutylene, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1616 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 150 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 34.8 g ofyellow grease.

1 g/5 to 10 ml CF₃ CFHCFHCF₂ CF₃ at r.t., largely soluble

Mw=12,500 by GPC in FC-75 at 80° C.

Mn=4,690 by GPC in FC-75 at 80° C.

Tg=-12.6° C. (second heat) by DSC 10° C./min under N₂

TGA, 10° C./min., N₂, 10% weight loss at ˜130° C.

Tm, none detected by DSC @10° C./min, N₂, second heat

Productivity 1.3 kg/L/hr (11 lbs/gal/hr)

Elemental Analysis, Found: 1.89% H, 1.78% H Calc.:* (TFE).sub.˜1.52x(HFP)₁.52x (C₄ H₈)_(x) 1.84% H

EXAMPLE 103 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₃ CH₂ CH₂ CH₂ OCF═CF₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,111 g TFE, 10 g n-butyl trifluorovinyl ether, and ˜1.2 g of NF₃ was madein 96.5 MPa reservoir (2). About 1748 g of this mixture were run throughthe 10 ml shaken autoclave at 250° C. and 96.5 MPa over a 150 minuteperiod. Drying the product for 4 hours under vacuum at 150° C. gave 28.8g of orange grease.

1 g/5 to 10 ml FC-75 at r.t., opalescent solution

Mw=17,500 by GPC in FC-75 at 80° C.

Mn=6,890 by GPC in FC-75 at 80° C.

Tg=-3° C. (second heat) by DSC @10° C./min under N₂

TGA, 10° C./min., N₂, 10% weight loss at ˜150° C.

Tm, none detected by DSC @10° C./min, N₂, second heat

Productivity 1.1 kg/L/hr (9.6 lbs/gal/hr)

Elemental Analysis, Found: 0.62% H, 0.65% H Calc:* (TFE).sub.˜5x(HFP).sub.˜5x (C₆ H₉ F₃ O)_(x) 0.64 % H

EXAMPLE 104 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHCF₂ CF₂ Br

The same set up was used as in Example 1. A mixture of 2000 g of HFP,114 g TFE, 14.5 g 4-bromo-3,3,4,4-tetrafluoro-1-butene, and ˜1.2 g ofNF₃ was made in 96.5 MPa reservoir (2). About 1678 g of this mixturewere run through the 10 ml shaken autoclave at 250° C. and 96.5 MPa overa 164 minute period. Drying the product under vacuum gave 86.7 g ofoff-white polymer, a 10.45 g sample of which was dried further for 4hours at 150° C. under vacuum, giving 8.9 g of colorless polymer.Results for the oven dried 8.9 g sample are gathered below.

1 g/5 ml FC-75 at r.t., clear solution

Mw=20,300 by GPC in FC-75 at 80° C.

Mn=7,290 by GPC in FC-75 at 80° C.

Tg=10° C. (second heat) by DSC @10° C./min under N₂

10% wt. loss in TGA @10° C./min under N₂ : 320° C.

Tm, none detected by DSC @10° C./min, N₂, second heat

Productivity 2.7 kg/L/hr (22 lbs/gal/hr)

Elemental Analysis, Found: 4.10% Br, 4.07% Br. Calc.:* (TFE).sub.˜7.02x(HFP).sub.˜7.02x (C₄ H₃ F₄ Br)_(x) 4.07% Br

EXAMPLE 105 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHOCH₃

The same set up was used as in Example 1. A mixture of 2000 g of HFP, 92g TFE, 5 g methyl vinyl ether, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1512 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 130 minute period.Drying the product under vacuum gave 46.9 g of tacky yellow grease, a13.44 g sample of which was dried further for 4 hours at 150° C. undervacuum, giving 11.48 g of grease unchanged in appearance. Results forthe oven dried 11.48 g sample are gathered below.

1 g/5 to 7 ml CF₃ CFHCFHCF₂ CF₃ at r.t., clear solution

Mw=7,940 by GPC in FC-75 at 80° C.

Mn=4,650 by GPC in FC-75 at 80° C.

10% wt. loss in TGA @10° C./min under N₂ : 200° C.

Productivity 1.4 kg/L/hr (12 lbs/gal/hr)

Elemental Analysis, Found: 0.94 & 0.93% H Calc.:*(TFE)˜2.4×(HFP)˜2.4×(C3H6O)×0.92% H

EXAMPLE 106 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/Perfluorocyclobutene

The same set up was used as in Example 1. A mixture of 2000 g of HFP,111 g TFE, 10 g perfluorocyclobutene, and ˜1.2 g of NF₃ was made in 96.5MPa reservoir (2). About 1739 g of this mixture were run through the 10ml shaken autoclave at 250° C. and 96.5 MPa over a 145 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 91.6 g ofcolorless polymer.

1 g/5 ml FC-75 at r.t., viscous hazy solution, some flocculent solids

Mw=213,000 by GPC in FC-75 at 80° C.

Mn=78,600 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 15 kg =0.8 g/min

Tg=30° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 420° C. @ 10C/min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

0.5 mole % perfluorocyclobutene by ¹⁹ F NMR in melt at 320° C.

40.9 mole % HFP by ¹⁹ F NMR in melt at 320° C.

58.6 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 3.8 kg/L/hr (31 lbs/gal/hr)

EXAMPLE 107 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/Perfluorocyclopentene

The same set up was used as in Example 1. A mixture of 2000 g of HFP,137 g TFE, 20 g perfluorocyclopentene, and ˜0.6 g of NF₃ was made in96.5 MPa reservoir (2). About 1578 g of this mixture were run throughthe 10 ml shaken autoclave at 350° C. and 96.5 MPa over a 110 minuteperiod. Drying the product under vacuum and then for four hours at 150°C. under vacuum gave 217.1 g of white polymer.

1 g/5 FC-75 at r.t., clear to hazy, trace flocculent solid

Mw=103,000 by GPC in FC-75 at 80° C.

Mn=30,600 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =1 g/min

Tg=29° C. (second heat) by DSC @ 10° C./min under N₂

10% weight loss temperature, 380° C., @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

0.6 mole % perfluorocyclopentene by ¹⁹ F NMR in melt at 320° C.

49.0 mole % HFP by ¹⁹ F NMR in melt at 320° C.

50.4 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 12 kg/L/hr (98 lbs/gal/hr)

EXAMPLE 108 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/Vinyl fluoride

The same set up was used as in Example 1. A mixture of 2000 g of HFP,111 g TFE, 10 g vinyl fluoride, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1663 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 135 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 91.6 g ofcolorless polymer.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃ at r.t., hazy solution

Mw=31,600 by GPC in FC-75 at 80° C. partial solubility)

Mn=12,800 by GPC in FC-75 at 80° C. (partial solubility)

Tg=9° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 370° C. @ 10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

16 mole % vinyl fluoride by ¹⁹ F NMR in melt at 320° C.

40 mole % HFP by ¹⁹ F NMR in melt at 320° C.

44 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 4.1 kg/L/hr (34 lbs/gal/hr)

EXAMPLE 109 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CF₂ ═C(CF₃)(C═O)F

The same set up was used as in Example 1. A mixture of 2000 g of HFP,115 g TFE, 10 g CF₂ ═C(CF₃)(C═O)F, and ˜0.6 g of NF₃ was made in 96.5MPa reservoir (2). About 1411 g of this mixture were run through the 10ml shaken autoclave at 300° C. and 96.5 MPa over a 125 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 152 g ofpale yellow polymer.

1 g/5 ml FC-75 at r.t., soluble, trace flocculent solids

Mw=138,000 by GPC in FC-75 at 80° C.

Mn=50,000 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =0.7 g/min

Tg=36° C. (second heat) by DSC @10° C./min under N₂

10% weight loss temperature 390° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min under N₂

˜0.1 mole % CF₂ ═C(CF₃)COF by ¹⁹ F NMR in melt at 320° C.

48.2 mole % HFP by ¹⁹ F NMR in melt at 320° C.

51.7 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 7.3 kg/L/hr (61 lbs/gal/hr)

EXAMPLE 110 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CF₂ ═CFH

The same set up was used as in Example 1. A mixture of 2000 g of HFP,111 g TFE, 10 g CF₂ ═CFH, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1622 g of this mixture were run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 150 minute period.Drying the product for 4 hours under vacuum at 150° C. gave 109.8 g ofcolorless polymer.

1 g/5 ml FC-75 at r.t., clear solution, trace (?) insolubles

Mw=185,000 by GPC in FC-75 at 80° C.

Mn=71,400 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =0-3 g/min

Tg=27° C. (second heat) by DSC @10° C./min under N₂

10% wt. loss temperature, 420° C. @10° C./min under N₂

Tm, none detected by DSC 810° C./min, N₂, second heat

7.8 mole % CF₂ ═CFH by ¹⁹ F NMR in melt at 320° C.

39.2 mole % HFP by ¹⁹ F NMR in melt at 320° C.

53.0 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 4.4 kg/L/hr (36 lbs/gal/hr)

EXAMPLE 111 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/Perfluoro-2-methylene-4-methyl-1,3-dioxolane

The same set up was used as in Example 1. A mixture of 2000 g of HFP,116 g TFE, 20 g perfluoro-2-methylene-4-methyl-1,3-dioxolane, and ˜0.6 gof NF₃ was made in 96.5 MPa reservoir (2). About 1471 g of this mixturewere run through the 10 ml shaken autoclave at 300° C. and 96.5 MPa overa 140 minute period. Drying the product for 4 hours under vacuum at 150°C. gave 156 g of colorless polymer.

1 g/5 ml FC-75 at r.t., hazy solution, flocculent residue

Mw=108,000 by GPC in FC-75 at 80° C.

Mn=39,400 by GPC in FC-75 at 80° C.

Melt index₁₂₀° C., 5 kg =1.1 g/min

Tg=31° C. (second heat) by DSC @10° C./min under N₂

10% wt. loss temperature, 370° C. @10° C./min under N₂

Tm, none detected by DSC @10° C./min under N₂

2.3 mole % perfluoro-2-methylene-4-methyl-1,3 dioxolane by ¹⁹ F NMR inmelt at 320° C.

46.0 mole % HFP by ¹⁹ F NMR in melt at 300° C.

51.7 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 6.7 kg/L/hr (56 lbs/gal/hr)

EXAMPLE 112 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 4000 g of HFP,100 g TFE, 100 g vinylidene fluoride, and ˜1.2 g of NF₃ was made in 96.5MPa reservoir (2). About 3771 g of this mixture were run through the 10ml shaken autoclave at 225° C. and 96.5 MPa over a 325 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 225 g of white polymer. Analysis results are shown below.

1 g/5 ml of CF₃ CFHCFHCF₂ CF₃, clear solution at room temperature

Mw=318,000 by GPC in FC-75 at 80° C.

Mn=100,000 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 15 kg =0.3 g/min

Tg=2° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by TGA @10° C./min under N₂

˜36 mole % VF2*

˜44 mole % HFP*

˜20 mole % TFE*

Productivity 4.2 kg/L/hr (35 lbs/gal/hr)

EXAMPLE 113 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 4000 g of HFP,200 g TFE, 5 g vinylidene fluoride, and ˜1.2 g of NF₃ was made in 96.5MPa reservoir (2). About 3932 g of this mixture were run through the 10ml shaken autoclave at 225° C. and 96.5 MPa over a 380 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 116 g of white polymer. Analysis results are shown below.

1 g/5 ml FC-75, clear, viscous solution at r.t.

Mw=428,000 by GPC in FC-75 at 80° C.

Mn=181,000 by GPC in FC-75 at 80° C.

Melt index₂₆₀° C., 15 kg =0.8 g/min

Tg=19° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by TGA 10° C./min under N₂

˜10 mole % VF2*

˜34 mole % HFP*

˜56 mole % TFE*

Productivity 1.8 kg/L/hr (15 lbs/gal/hr)

EXAMPLE 114 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/VF2

A. At 225° C.: The same set up was used as in Example 1. A mixture of2000 g of HFP, 80 g vinylidene fluoride, and ˜1.2 g of NF₃ was made in96.5 MPa reservoir (2). About 1600 g of this mixture were run throughthe 10 ml shaken autoclave at 225° C. and 96.5 WPa over a 135 minuteperiod. Drying the product first under vacuum and then for 4 hours at150° C. gave 82 g of white polymer. Analysis results are shown below.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃ at r.t., clear, highly viscous

Inherent Viscosity in CF₃ CFHCFHCF₂ CF₃ at 25° C.=0.578

Tg=2° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 430° C. by TGA @10° C./min under N₂

˜53 mole % VF2 by ¹⁹ F NMR in melt at 300° C.

˜47 mole % HFP by ¹⁹ F NMR in melt at 300° C.

Productivity 3.6 kg/L/hr (30 lbs/gal/hr)

B. At 200° C.: The same set up was used as in Example 1 A mixture of2000 g of HFP, 80 g vinylidene fluoride, and ˜1.2 g of NF₃ was made in96.5 MPa reservoir (2). About 1681 g of this mixture were run throughthe 10 ml shaken autoclave at 200° C. and 96.5 MPa over a 110 minuteperiod. Drying the product first under vacuum and then for 4 hours at150° C. gave 38 g of white polymer. Analysis results are shown below.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃ at r.t., clear, highly viscous

Inherent Viscosity in CF₃ CFHCFHCF₂ CF₃ at 25° C.=0.793

Tg=0° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC by TGA @10° C./min, N₂, second heat

10% weight loss temperature 430° C. @10° C./min under N₂

˜55 mole % VF2 by ¹⁹ F NMR in melt at 300° C.

˜45 mole % HFP by ¹⁹ F NMR in melt at 300° C.

Productivity 2.1 kg/L/hr (17 lbs/gal/hr)

EXAMPLE 115 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHO(C═O)CF₃

A. 225° C.: The same set up was used as in Example 1. A mixture of 4000g of HFP, 220 g TFE, 5 g vinyl trifluoroacetate, and ˜2.3 g of NF₃ wasmade in 96.5 MPa reservoir (2). About 4046 g of this mixture were runthrough the 10 ml shaken autoclave at 225° C. and 96.5 MPa over a 300minute period. Drying the product first under vacuum and then for 4hours at 150° C. gave 147 g of white polymer. Analysis results are shownbelow.

1 g/5 ml FC-75, soluble with trace of flocculent solid

Mw=151,000 by GPC in FC-75 at 80° C.

Mn=49,500 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 5 kg =4 g/min

Tg=14° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 380° C. by DSC @10° C./min under N₂

˜3.0 mole % CH₂ ═CHO(C═O)CF₃ by ¹⁹ F NMR in melt at 340° C.

˜34.1 mole % HFP by ¹⁹ F NMR in melt at 340° C.

˜62.9 mole % TFE by ¹⁹ F NMR in melt at 340° C.

Productivity 2.9 kg/L/hr (24 lbs/gal/hr)

B. 200° C.: The same set up was used as in Example 1. A mixture of 4200g of HFP, 220 g TFE, 5 g vinyl trifluoroacetate, and ˜2.3 g of NF₃ wasmade in 96.5 MPa reservoir (2). About 4109 g of this mixture was runthrough the 10 ml shaken autoclave at 200° C. and 96.5 MPa over a 390minute period. Drying the product first under vacuum and then for 4hours at 150° C. gave 84 g of white polymer. Analysis results are shownbelow.

1 g/5 ml FC-75, soluble with trace of flocculent solid

Mw=214,000 by GPC in FC-75 at 80° C.

Mn=65,900 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 5 kg =1.3 g/min

Tg=24° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 400° C. by DSC 10° C./min under N₂

˜4.3 mole % CH₂ ═CHO(C═O)CF₃ by ¹⁹ F NMR in melt at 320° C.

˜31.0 mole % HFP by ¹⁹ F NMR in melt at 320° C.

˜64.7 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 1.3 kg/L/hr (11 lbs/gal/hr)

EXAMPLE 116 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CFH═CF₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, 20 g trifluoroethylene, and -1.2 g of NF₃ was made in 96.5MPa reservoir (2). About 1694 g of this mixture was run through the 10ml shaken autoclave at 200° C. and 96.5 MPa over a 145 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 54 g of white polymer. Analysis results are gathered below.

1 g/10 ml FC-75, very viscous, incomplete solution

Mw=613,000 by GPC in FC-75 at 80° C.

Mn=137,000 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 15 kg =0.7 g/min

Tg=25° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by DSC @10° C./min under N₂

˜20.0 mole % CHF═CF₂ by ¹⁹ F NMR in melt at 250° C.

˜28.1 mole % HFP by ¹⁹ F NMR in melt at 250° C.

˜51.9 mole % TFE by ¹⁹ F NMR in melt at 250° C.

Productivity 2.2 kg/L/hr (19 lbs/gal/hr)

EXAMPLE 117 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHF

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, 20 g vinyl fluoride, and ˜1.2 g of NF₃ was made in 96.5 MPareservoir (2). About 1752 g of this mixture was run through the 10 mlshaken autoclave at 200° C. and 96.5 MPa over a 135 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 59 g of white polymer. Analysis results are gathered below.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃ highly viscous, hazy solution

Melt index₁₆₀° C., 15 kg =0.5 g/min

Tg=10° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by DSC @10° C./min under N₂

˜34.1 mole % CH₂ ═CHF by ¹⁹ F NMR in melt at 300° C.

˜31.9 mole % HFP by ¹⁹ F NMR in melt at 300° C.

˜34.0 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 2.6 kg/L/hr (22 lbs/gal/hr)

EXAMPLE 118 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/FSO₂ CF₂ CF₂ OCF(CF₃)CF₂ OCF═CF₂ (PSEPVE)

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, 50 g PSEPVE, and ˜1.2 g of NF₃ was made in 96.5 MPa reservoir(2). About 1857 g of this mixture was run through the 10 ml shakenautoclave at 200° C. and 96.5 MPa over a 165 minute period. The initialproduct was a thick fluid. Drying the product first under vacuum andthen for 4 hours at 150° C. gave 21 g of polymer. Analysis results areshown below.

1 g/5 ml of FC-75, partial solution at room temperature

Mw=97,700 by GPC in FC-75 at 80° C.

Mn=20,200 by GPC in FC-75 at 80° C.

Tg=17° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

¹⁹ F NMR in Hexafluorobenezene solution at 80° C.

˜1.4 mole % PSEPVE as free monomer

˜1.4 mole % PSEPVE terpolymerized

˜27.6 mole % HFP terpolymerized

˜69.6 mole % TFE terpolymerized

Productivity 0.8 kg/L/hr (6.5 lbs/gal/hr)

EXAMPLE 119 Continuous Polymerization in 10 ml Autoclave with AgitationCF₃ CF₂ CF₂ CF₂ N═NCF₂ CF₂ CF₂ CF₃ Initiation

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, and 0.7 g of CF₃ CF₂ CF₂ CF₂ N═NCF₂ CF₂ CF₂ CF₃ dissolved in2 ml HFP cyclic dimer (perfluorodimethylcyclobutane) was made in 96.5MPa reservoir (2). About 1760 g of this mixture was run through the 10ml shaken autoclave at 350° C. and 96.5 MPa over a 145 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 120 g of white polymer. Analysis results are shown below.

1 g/5 ml of FC-75, clear solution, trace flocculent solid

Mw=174,000 by GPC in FC-75 at 80° C.

Mn=62,200 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 5 kg =0.9 g/min

Tg=31° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 400° C. by DSC @10° C./min under N₂

˜47 mole % HFP by ¹⁹ F NMR in melt at 320° C.

˜53 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 5.0 kg/L/hr (41 lbs/gal/hr)

EXAMPLE 120 Continuous Polymerization in 10 ml Autoclave with AgitationCF₃ CF₂ CF₂ OCF(CF₃)SO₂ (CF₂)₇ CF₃ Initiation

A. 65.5 MPa: The same set up was used as in Example 1. A mixture of 2000g of HFP, 110 g TFE, and 2.5 g of CF₃ CF₂ CF₂ OCF(CF₃)SO₂ (CF₂)₇ CF₃dissolved in 2 ml HFP cyclic dimer (perfluorodimethylcyclobutane) wasmade in 96.5 MPa reservoir (2). About 1674 g of this mixture was runthrough the 10 ml shaken autoclave at 350° C. and 62.3 to 70.5 MPa(˜65.5 MPa average) over a 110 minute period. Drying the product firstunder vacuum and then for 4 hours at 150° C. gave 120 g of whitepolymer. Analysis results are shown below.

1 g/5 ml of FC-75, partial solubility at room temperature

Mw=125,000 by GPC in FC-75 at 80° C.

Mn=56,600 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 5 kg =1.6 g/min

Tg=27° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by DSC @10° C./min under N₂

˜44 mole % HFP by ¹⁹ F NMR in melt at 320° C.

˜56 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 6.5 kg/L/hr (54 lbs/gal/hr)

B. 96.5 MPa: The same set up was used as in Example 1. A mixture of 2000g of HFP, 110 g TFE, and 2.5 g of CF₃ CF₂ CF₂ OCF(CF₃)SO₂ (CF₂)₇ CF₃dissolved in 2 ml HFP cyclic dimer (perfluorodimethylcyclobutane) wasmade in 3.8 L reservoir (2). About 1552 g of this mixture was runthrough the 10 ml shaken autoclave at 350° C. and 96.5 MPa over a 140minute period. Drying the product first under vacuum and then for 4hours at 150° C. gave 148 g of white polymer. Analysis results are shownbelow.

1 g/5 ml of FC-75, clear solution, trace flocculent solid

Mw=115,000 by GPC in FC-75 at 80° C.

Mn=53,400 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 5 kg =2.7 g/min

Tg=29° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 410° C. by DSC @10° C./min under N₂

42 mole % HFP by ¹⁹ F NMR in melt at 300° C.

58 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 6.3 kg/L/hr (53 lbs/gal/hr)

EXAMPLE 121 Preparation of Perfluoro-1-propoxyethyl octyl sulfone CF₃ C₂CF₂ OCF(CF₃)SO₂ (CF₂)₇ CF₃

A solution of perfluoro-1-propoxyethanesulfonyl fluoride (18.6 g, 50.4mmol, perfluoro-1-propoxyethanesulfonyl fluoride was prepared by themethod of S. Temple, J. Org. Chem. 1968, 33, 344) andperfluorooctyltrimethylsilane (11.8 g, 24 mmol,perfluorooctyltrimethylsilane was prepared as described in U.S. Pat. No.5,171,893) in trifluorotoluene (24 mL) was cooled to ca. -11° C. andtreated with tris(piperidino)sulfonium benzoate (144 mg, 0.35 mmol). Thereaction was allowed to warm slowly to 25° C. After 0.5 hr, another 144mg of tris(piperidino)sulfonium benzoate was added, resulting inadditional color and a mild exotherm. After stirring for 18 hr.,volatile components were transferred from the vessel under vacuum,collecting solvent first, then higher boiling material which wasredistilled to afford 6.8 g (37%) of product with bp=4547° C./0.05 mm Hgwhich was homogeneous by gas chromatographic analysis. ¹⁹ F NMR(THF-d₈): -77.2 (m), -80.7 (m), -81.3 (t, J=10 Hz), -81.67 (t, J=7.3Hz), -104.4 and -105.4 (AB pattern, J=246 Hz), singlets at -119.5,-121.4, -121.7, -121.95, -122.8, -123.8, -126.3, and -129.4, in accordwith the desired structure, CF₃ CF₂ CF₂ OCF(CF₃)SO₂ (CF₂)₇ CF₃.

EXAMPLE 122 Continuous Polymerization in 10 ml Autoclave with AgitationCF₃ CF₂ CF₂ OCF(CF₃)SO₂ F Initiation

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, and 1.2 g of CF₃ CF₂ CF₂ OCF(CF₃)SO₂ F dissolved in 2 ml HFPcyclic dimer (perfluorodimethylcyclobutane) was made in 3.8 L reservoir(2). About 1604 g of this mixture was run through the 10 ml shakenautoclave at 350° C. and 96.5 MPa over a 135 minute period. Drying theproduct first under vacuum and then for 4 hours at 150° C. gave 80 g ofwhite polymer. Analysis results are shown below.

1 g/5 ml of FC-75, clear solution at room temperature

Mw=343,000 by GPC in FC-75 at 80° C.

Mn=106,000 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 15 kg =0.3 g/min

Tg=32° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 420° C. by DSC @10° C./min under N₂

˜45 mole % HFP by ¹⁹ F NMR in melt at 320° C.

˜55 mole % TFE by ¹⁹ F NMR in melt at 320° C.

Productivity 3.6 kg/L/hr (30 lbs/gal/hr)

EXAMPLE 123 Continuous Polymerization in 10 ml Autoclave with AgitationCF₃ CF₂ CF₂ CF₂ SO₂ Cl Initiation

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, and 1 g of CF₃ CF₂ CF₂ CF₂ SO₂ Cl dissolved in 2 ml HFPcyclic dimer (perfluorodimethylcyclobutane) was made in reservoir (2).About 1585 g of this mixture was run through the 10 ml shaken autoclaveat 350° C. and 14,000 over a 140 minute period. Drying the product firstunder vacuum and then for 4 hours at 150° C. gave 94 g of perhapsslightly gray polymer. Analysis results are shown below.

1 g/5 ml of FC-75, clear solution with trace of flocculent solid

Mw=276,000 by GPC in FC-75 at 80° C.

Mn=76,100 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 15 kg =0.9 g/min

Tg=31° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 410° C. by DSC @10° C./min under N₂

46 mole % HFP by ¹⁹ F NMR in melt at 300° C.

54 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 4.0 kg/L/hr (33 lbs/gal/hr)

EXAMPLE 124 Continuous Polymerization in 10 ml Autoclave with AgitationClSO₂ Cl Initiation

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, and 1 g of ClSO₂ Cl dissolved in 2 ml HFP cyclic dimer(perfluorodimethylcyclobutane) was made in reservoir (2). About 1620 gof this mixture was run through the 10 ml shaken autoclave at 300° C.and 96.5 MPa over a 155 minute period. Drying the product first undervacuum and then for 4 hours at 150° C. gave 63 g of polymer. Analysisresults are shown below.

1 g/5 ml of FC-75, clear solution at room temperature

Mw=319,000 by GPC in FC-75 at 80° C.

Mn=111,000 by GPC in FC-75 at 80° C.

Melt index₁₆₀° C., 15 kg =1.3 g/min

Tg=32° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 410° C. by DSC @10° C./min under N₂

42 mole % HFP by ¹⁹ F NMR in melt at 300° C.

58 mole % TFE by ¹⁹ F NMR in melt at 300° C.

Productivity 2.4 kg/L/hr (20 lbs/gal/hr)

EXAMPLE 125 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CHCH₂ Si(OMe)₃

The same set up was used as in Example 1. A mixture of 4000 g of HFP,220 g TFE, 4 ml of allyltrimethoxysilane, and ˜2.3 g of NF₃ was made inreservoir (2). About 3919 g of this mixture was run through the 10 mlshaken autoclave at 225° C. and 96.5 MPa over a 330 minute period.Drying the product under vacuum at room temperature gave 99 g of whitepolymer. A melt index at 100° C. with a 5 kg weight gave a flow of 1.6g/min, but after exposing 8 g of polymer to 25 ml water+1 ml CF₃ COOHfirst at r.t. and then at reflux, a temperature of 160° C. was needed toobtain comparable flow rates, 2 g/min with a 5 kg weight. Compositionwas determined by ¹⁹ F NMR on the polymer melt at 320° C., using theCF(CF3)CH₂ peak at 77 ppm to estimate a minimum allyltrimethoxysilanecontent. Fluorine NMR also found peaks for --CFH-- groups at 208-212ppm, which if calculated as a monomer unit, would make up 2.2 mole %(0.61 wt %) of the polymer. Analytical results are shown below.

1 g/5 ml of FC-75, partial, hazy solution at room temperature

Mw=51,800 by GPC in FC-75 at 80° C.

Mn=14,900 by GPC in FC-75 at 80° C.

Melt index₁₀₀° C., 5 kg =1.6 g/min

Tg=10° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

≧˜4.2 mole % allyltrimethoxysilane by ¹⁹ F NMR in melt at 320° C.*

≦32.6 mole % HFP by ¹⁹ F NMR in melt at 320° C.

≦61.0 mole % TFE by ¹⁹ F NMR in melt at 320° C.

≦2.2 mole % --CFH-- by ¹⁹ F NMR in melt at 320° C.

Productivity 1.8 kg/L/hr (15 lbs/gal/hr)

EXAMPLE 126 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/CH₂ ═CH(C═O)OCH(CF₃)₂

The same set up was used as in Example 1. A mixture of 2000 g of HFP,110 g TFE, and 5 g of 1,1,1,3,3,3-hexafluoroisopropyl acrylate was madein reservoir (2). About 1276 g of this mixture was run through the 10 mlshaken autoclave at 250° C. and 96.5 MPa over a 140 minute period.Drying the product first under vacuum and then for 4 hours at 150° C.gave 85.9 g of polymer. Analysis results are shown below.

1 g/5 ml FC-75, soluble with trace of flocculent residue at r.t.

Mw=84,700 by GPC in FC-75 at 80° C.

Mn=27,600 by GPC in FC-75 at 80° C.

Tg=27° C. (second heat) by DSC @10° C./min under N₂

Tm, none detected by DSC @10° C./min, N₂, second heat

10% weight loss temperature 390° C. by TGA @10° C./min under N₂

˜3.2 mole % CH₂ ═CH(C═O)OCH(CF₃)₂ by ¹⁹ F NMR in melt at 250° C.*

˜39.9 mole % HFP by ¹⁹ F NMR in melt at 250° C.

˜56.9 mole % TFE by ¹⁹ F NMR in melt at 250° C.

Productivity 3.6 kg/L/hr (31 lbs/gal/hr) -186 ppm.

EXAMPLE 127 Perfluorosulfur Compounds as Solvents for AmorphousFluoropolymers

A. Perfluoro-1,4-dithiane: A 0.1009 g sample of 44:56 poly(HFP:TFE),Mw=156,000, was rolled in a vial with 1 ml (1.64 g) ofperfluoro-1,4-dithiane for 2 hours at room temperature giving asolution.

B. Perfluorothiepane: A 0.2305 g sample of 42:58 poly(HFP:TFE),Mw=74,000, was rolled in a vial with 1 ml (1.78 g) of perfluorothiepanefor 24 hours at room temperature giving a viscous solution.

C. Perfluorodiethylsulfone: A 0.1 g sample of 45:55 poly(HFP:TFE),Mw=325,000, was rolled in a vial with 1 ml of perfluorodiethylsulfonefor 24 hours at room temperature giving a viscous solution.

D. Perfluoroctanesulfonyl fluoride: A 0.5 g sample of 46:54poly(HFP:TFE), Mw=392,000, was rolled in a vial with 5 ml ofperfluorooctanesulfonyl fluoride giving a clear solution at roomtemperature. Another 0.5 g of polymer was added, going again intosolution, but now very viscous.

EXAMPLE 128 The Use of Mixed Solvents

A. FC-75 and HFC's: A 1 g sample of 44:56 poly(HFP/TFE), Mw=285,000 wasdissolved in 5 ml of FC-75. About 6 to 7 ml of CF₃ CFHCFHCF₂ CF₃ had tobe added with stirring before there was any sign of persistent haze orprecipitate.

A 1 g sample of 45:55 poly(HFP/TFE), Mw=325,000 was dissolved in 5 ml ofFC-75. About 6 to 7 ml of CF₃ CF₂ CF₂ OCFHCF₃ had to be added withstirring before there was any sign of persistent haze or precipitate.

B. Perfluorooctane and HCFC's: A 0.58 g sample of 45:55 poly(HFP/TFE),Mw=325,000 was dissolved in 5 ml of perfluoroalkane (˜perfluorooctane).About 6 to 8 ml of CF₃ CHCl₂ had to be added with stirring before therewas any sign of persistent haze or precipitate.

EXAMPLE 129

Aluminum coupons 2.5 cm×7.6 cm×0.64 mm were cleaned by washing withacetone and were dried for 1 h at 150° C. A solution of a 51 wt. %HFP/49 wt. % TFE copolymer (combined sample from Examples 1 to 13) wasprepared by dissolving 1 g polymer in 99 g PF5080 solvent (3M Co.,Minneapolis, Minn., U.S.A., believed to be perfluorooctane). Two coatsof solution were applied at room temperature to the surface of thecleaned aluminum coupons by spraying the solution with an air brush at207 kPa (absolute). The coatings were each dried and annealed for 4 h at250° C. in an air circulating oven.

One fluoropolymer coated coupon and one clean uncoated coupon wereplaced in a freezer at -17° C. with three drops of water on each, onedrop near each end and one drop in the center. After 4.75 h one dropnear each end and one drop in the center. After 4.75 h the coupons wereremoved from the freezer and were immediately tested for adhesion of thefrozen droplets to the metal by trying to peel the drops off of thesurface with a thumb nail. The frozen droplets on the uncoated controlwere very difficult to remove. The frozen droplets on the fluoropolymercoated coupons fell off with very little force.

EXAMPLE 130

Aluminum cylinders 1.3 cm diameter×7.6 cm length were cleaned by washingwith acetone and were dried for 1 h at 150° C. The fluoropolymersolution used in Example 129 was used to coat one cylindrical surface.Two coats of solution were applied at room temperature to the surface ofthe cleaned aluminum cylinder by spraying the solution with an air brushat 207 kPa (absolute). The coatings were each dried and annealed for 4 hat 250° C. in an air circulating oven.

One fluoropolymer coated cylinder and one clean uncoated cylinder wereplaced in a wind tunnel at -4° C. and with air stream velocity of 67.1m/sec. Droplets of water, 5 μm in diameter were sprayed into the airstream for 5.8 min. The supercooled droplets built up a horse shoeshaped ice formation, approximately 1.0 cm thick on both cylinders.

The ice coated cylinders were removed from the chamber. A flat scraperwith an attached force gauge was used to immediately remove the ice fromthe cylinders. The force required to scrape the ice from the control,uncoated cylinder was 5.7 N. The force required to scrape the ice fromthe fluoropolymer coated cylinder was 0.64 N.

The cylinders were then placed back into the wind tunnel and the icecoating test repeated two more times. After the third exposure, theforce required to scrape the ice from the control, uncoated cylinder was6.2 N. The ice fell off the fluoropolymer coated as being removed fromthe chamber, with no applied scraping force.

EXAMPLE 131

Under the same testing protocol as for Example 130 above, a 40.6 mole %HFP/56.5 mole % TFE/2.9 mole % CTFE terpolymer (from Example 91) took3.1 N and 4.1 N of force to scrape the ice from the test cylinder.

EXAMPLE 132

In this Example copolymers containing VF2 are analyzed for partialsequence distribution. Sequences are denoted by the Sequence No., asdescribed above. Analyses were also done in solution as described abovefor these sequences.

The polymers analyzed are as follows. Polymer C is a VF2/HFP dipolymerprepared in Example 114A, while Polymer D is a VF2/HFP/TFE tripolymerprepared in Example 112. Viton® A and Viton® B fluoroelastomers arecommercially available from E. I. du Pont de Nemours and Company,Wilmington, Del., U.S.A., and are made by relatively (compared to theconditions for polymerizations herein) low temperature and low pressurefree radical polymerization in aqueous emulsion.

In the Table below the compositions of these polymers are shown,together with partial sequence distributions.

    ______________________________________                                        Polymer                                                                         Composition, mole % C Viton ® A D Viton ® B                         ______________________________________                                          VF2 53.5 78.0 36.0 61.0                                                       HFP 46.5 22.0 44.0 17.0                                                       TFE -- -- 20.0 22.0                                                         ______________________________________                                        Sequence No. Mole Percent                                                     ______________________________________                                        1 + 2        12.8    5.9       10.9  8.8                                        3 + 4 10.6 67.1  4.1 38.3                                                     5 76.6 27.0 85.0 52.9                                                       ______________________________________                                    

EXAMPLE 133 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/VF2

The same set up was used as in Example 1. A mixture of 2000 g HFP, 320 gVF2, and .sup.˜ 1.2 g of NF₃ was made in reservoir (2). About 399 g ofthis mixture were run through the 10 ml shaken autoclave at 250° C. and96.5 MPa over a 35 minute period, the run being terminated early becauseof the product collector's having been filled with large volumes ofpolymeric foam. A brief exotherm to 310° C. was noted near the exit ofthe reactor. Drying the product first under vacuum at room temperatureand then at 150° C. gave 102 g of polymer.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃, clear solution at room temperature

Inherent viscosity in CF₃ CFHCFHCF₂ CF₃ at 25° C.=0.108

48.9 mole % VF2 by ¹³ C NMR

51.1 mole % HFP by ¹³ C NMR

Productivity 17.4 kg/L/hr (145 lbs/gal/hr)

Sequence analysis by ¹³ C NMR for S1 is given in the Table after Example136.

EXAMPLE 134 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/VF2

The same set up was used as in Example 1. A mixture of 1000 g HFP, 200 gVF2, 200 ml CF₃ CFHCFHCF₂ CF₃, and .sup.˜ 1.2 g of NF₃ was made inreservoir (2). About 831 g of this mixture were run through the 10 mlshaken autoclave at 200° C. and 96.5 MPa over a 75 minute periodproducing a thick, semi-liquid mix. Evaporating the CF₃ CFHCFHCF₂ CF₃followed by drying first under vacuum at room temperature and then at150° C. gave 17.3 g of elastomeric polymer.

Mw=1,000,000 by GPC in tetrahydrofuran

Mn=27,600 by GPC in tetrahydrofuran

69.8 mole % VF2 by ¹³ C NMR

30.2 mole % HFP by ¹³ C NMR

Productivity 1.4 kg/L/hr (12 lbs/gal/hr)

Sequence analysis by ¹³ C NMR for S1 is given in the Table after Example136.

EXAMPLE 135 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 2000 g HFP, 290 gVF2, 30 g TFE, and .sup.˜ 1.2 g of NF₃ was made in reservoir (2). About691 g of this mixture were run through the 10 ml shaken autoclave at250° C. and 96.5 MPa over a 60 minute period, the run being terminatedearly because of the product collector's having been filled with largevolumes of polymeric foam. A brief exotherm to 305° C. was observed nearthe outlet of the reactor. Drying the product first under vacuum at roomtemperature and then at 150° C. gave 169 g of polymer.

1 g/5 ml CF₃ CFHCFHCF₂ CF₃, clear solution at room temperature

Inherent viscosity in CF₃ CFHCFHCF₂ CF₃ at 25° C.=0.138

48.0 mole % VF2 by ¹³ C NMR

44.9 mole % HFP by ¹³ C NMR

7.1 mole % TFE by ¹³ C NMR

Productivity 16.8 kg/L/hr (141 lbs/gal/hr)

Sequence analysis by ¹³ C NMR for S1 is given in the Table after Example136.

EXAMPLE 136 Continuous Polymerization in 10 ml Autoclave with AgitationHFP/TFE/VF2

The same set up was used as in Example 1. A mixture of 1000 g HFP, 320 gVF2, 20 g TFE, and .sup.˜ 0.6 g of NF₃ was made in reservoir (2). About750 g of this mixture were run through the 10 ml shaken autoclave at250° C. and 96.5 MPa over a 60 minute period with no heat to thepreheater. A brief exotherm to 245° C. was observed near the outlet ofthe reactor. The semisolid product was dissolved up in .sup.˜ 500 ml CF₃CFHCFHCF₂ CF₃, treated with activated charcoal and filtered through abed of activated alumina. Excess solvent was evaporated and the polymerthen dried first under vacuum at room temperature and then at 150° C.giving 54.1 g of orange gum

1 g/5 ml CF₃ CFHCFHCF₂ CF₃, clear solution at room temperature

Inherent viscosity in CF₃ CFHCFHCF₂ CF₃ at 25° C.=0.107

56.9 mole % VF2 by ¹³ C NMR

33.6 mole % HFP by ¹³ C NMR

9.5 mole % TFE by ¹³ C NMR

Productivity 5.4 kg/L/hr (45 lbs/gal/hr)

Sequence analysis by ¹³ C NMR for S1 is given in the Table after thisexample.

                  TABLE                                                           ______________________________________                                        Ex. No. Mole % VF2                                                                              Mole % HFP  Mole % TFE                                                                            % S1                                    ______________________________________                                        133     48.9      51.1        --      1.6                                       134 69.8 30.2 -- 6.3                                                          135 48 44.9 7.1 1.5                                                           136 56.9 33.6 9.5 4.5                                                         Viton ® A 80.6 19.4 -- 3.8                                                Viton ® B 69.9 16.2 13.9  2.9                                           ______________________________________                                    

What is claimed is:
 1. A film comprising a polymer selected from thegroup consisting of:(A) an amorphous polymer, consisting essentially of,repeat units of the formula:(i) at least about 30 mole percent of

    --CF(CF.sub.3)--CF.sub.2 --                                (I)

(ii) at least about 1 mole percent

    --CF.sub.2 --CF.sub.2 --                                   (II)

(iii) 0 to about 10 mole percent ##STR2## wherein X is --C_(n) F_(2n+1)or --OC_(n) F_(2n+1), m is 2, 3 or 4, and n is an integer of 2 to 20,with --C_(n) F_(2n+1) or an integer of 1 to 20 with --OC_(n) F_(2n+1) ;and provided that in said polymer less than 20 mole percent of (I) ispresent in the form of triads; and; (B) an amorphous polymer containingrepeat units derived from:2- 60mole percent hexafluoropropylene, up to35 mole percent total of one or more second monomers, and the balancetetrafluoroethylene, provided that at least one mole percent of TFE ispresent in the polymer, and wherein said second monomer is ethylene,vinyl fluoride, trifluoroethylene, 3,3,3-trifluoropropene,2,3,3,3-tetrafluoropropene, 4-bromo-3,3,4,4-tetrafluoro-1-butene,ethylene CH₂ ═CHO(C═O)R² wherein R² is perfluoro-n-alkyl containing 1 to8 carbon atoms, CH₂ ═CHR³ wherein R³ is perfluoro-n-alkyl containing 1to 8 carbon atoms, CH₂ ═CH(C═O)OR⁴ wherein R⁴ is C_(n) F_(x) H_(y)wherein x+y=2n+1 and n is 1 to 8, chlorotrifluoroethylene, orallyltrimethoxysilane, and provided that at least some of said repeatunits derived from said second monomer are present; or 27-60 molepercent hexafluoropropylene, up to 5 mole percent total of one or morefourth monomers and the balance tetrafluoroethylene, provided that thepolymer contains at least 1 mole percent tetrafluoroethylene, whereinsaid fourth monomer is perfluorocyclopentene, perfluorocyclobutene, CF₂═CFCF₂ CN, CF₂ ═CFR⁵ wherein R⁵ is perfluoroalkyl optionally containingone or more of one or more ether groups, one cyano group, or onesulfonyl fluoride group, perfluoro(2-metylene-4-methyl-1,3-dioxolane),perfluoro(2-methyl-2,3-dihydro-1,4-dioxin), or FSO₂ CF₂ CF₂ OCF(CF₃)CF₂OCF═CF₂, and provided that at least some of said repeat units derivedfrom said fourth monomer are present; or 27-60 mole percenthexafluoropropylene, up to 30 mole percent total of one or more secondmonomers and up to 5 mole percent total of one or more fourth monomers,and the balance tetrafluoroethylene, provided that the polymer containsat least 1 mole percent tetrafluoroethylene, and further provided thatat least some repeat units derived from said second monomer and saidfourth monomer are present.
 2. A coating of a polymer selected from thegroup consisting of(A) an amorphous polymer, consisting essentially of,repeat units of the formula:(i) at least about 30 mole percent of

    --CF(CF.sub.3)--CF.sub.2 --                                (I)

(ii) at least about 1 mole percent

    --CF.sub.2 --CF.sub.2 --                                   (II)

(iii) 0 to about 10 mole percent ##STR3## wherein X is --C_(n) F_(2n+1)or -OC_(n) F_(2n+1), m is 2, 3 or 4 and n is an integer of 2 to 20, withC_(n) F_(2n+1) or an integer of 1 to 20 with --OC_(n) F_(2n+1) ; andprovided that in said polymer less than 20 mole percent of (I) ispresent in the form of triads; and; (B) an amorphous polymer containingrepeat units derived from:27-60 mole percent hexafluoropropylene, up to35 mole percent total of one or more second monomers, and the balancetetrafluoroethylene, provided that at least one mole percent of TFE ispresent in the polymer, and wherein said second monomer is ethylene,vinyl fluoride, trifluoroethylene, 3,3,3-trifluoropropene,2,3,3,3-tetrafluoropropene, 4-bromo-3,3,4,4-tetrafluoro-1-butene,ethylene CH₂ ═CHO(C═O)R² wherein R² is perfluoro-n-alkyl containing 1 to8 carbon atoms, CH₂ ═CHR³ wherein R³ is perfluoro-n-alkyl containing 1to 8 carbon atoms, CH₂ ═CH(C═O)OR⁴ wherein R⁴ is C_(n) F_(x) H_(y)wherein x+y=2n+1 and n is 1 to 8, chlorotrifluoroethylene, orallyltrimethoxysilane, and provided that at least some of said repeatunits derived from said second monomer are present; or 27-60 molepercent hexafluoropropylene, up to 5 mole percent total of one or morefourth monomers and the balance tetrafluoroethylene, provided that thepolymer contains at least 1 mole percent tetrafluoroethylene, whereinsaid fourth monomer is perfluorocyclopentene, perfluorocyclobutene, CF₂═CFCF₂ CN, CF₂ ═CFR⁵ wherein R⁵ is perfluoroalkyl optionally containingone or more of one or more ether groups, one cyano group, or onesulfonyl fluoride group, perfluoro(2-methylene-4-methyl-1,3-dioxolane),perfluoro(2-methyl-2,3-dihydro-1,4-dioxin), or FSO₂ CF₂ CF₂ OCF(CF₃)C₂OCF═CF₂, and provided that at least some of said repeat units derivedfrom said fourth monomer are present; or 27-60 mole percenthexafluoropropylene, up to 30 mole percent total of one or more secondmonomers and up to 5 mole percent total of one or more fourth monomers,and the balance tetrafluoroethylene, provided that the polymer containsat least 1 mole percent tetrafluoroethylene, and further provided thatat least some repeat units derived from said second monomer and saidfourth monomer are present.
 3. An encapsulant of a polymer selected fromthe group consisting of polymers (A) and (B) of claim
 1. 4. A solutionof a polymer selected from the group consisting of polymers (A) and (B)of claim
 1. 5. A fabric coated with a polymer selected from the groupconsisting of polymers (A) and (B) of claim
 1. 6. An object coated orencapsulated with a polymer selected from the group consisting ofpolymers (A) and (B) of claim
 1. 7. A mold release comprising a polymerselected from polymers (A) and (B) of claim
 1. 8. A mold or extrusiondie coated with a polymer selected from polymers (A) and (B) of claim 1.9. A blend of a polyolefin and a polymer selected from the groupconsisting of polymers (A) and (B) of claim 1, wherein the polymerselected is about 50 to about 1,000 parts per million by weight of thetotal of said polyolefin and said polymer selected.
 10. A polymerselected from the group consisting of polymers (A) and (B) of claim 1which is crosslinked.
 11. The solution as recited in claim 4 wherein asolvent is a mixed solvent.